Chemistry › Organic Chemistry

Cyclopropane Reaction Mechanisms

Works Count: 47428

Wikipedia

Description

This cluster of papers focuses on the catalytic carbene chemistry in organic synthesis, particularly on the use of donor-acceptor cyclopropanes, diazo compounds, and metal-catalyzed reactions. It covers topics such as enantioselective synthesis, site-selective functionalization, and the development of artificial metalloenzymes for carbene transfer reactions.

Keywords

Carbene Chemistry; Cyclopropanation; Metal-Catalyzed Reactions; Donor-Acceptor Cyclopropanes; Enantioselective Synthesis; Rhodium-Catalyzed Reactions; Diazo Compounds; Artificial Metalloenzymes; Site-Selective Functionalization; Transition-Metal Chemistry

Modern Organic Synthesis with α-Diazocarbonyl Compounds

2015-08-18

Alan Ford , Hugues Miel , Aoife Ring +3 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTModern Organic Synthesis with α-Diazocarbonyl CompoundsAlan Ford†, Hugues Miel§, Aoife Ring†, Catherine N. Slattery†, Anita R. Maguire*†‡, and M. Anthony McKervey*∥View Author Information† ‡ †Department of Chemistry … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTModern Organic Synthesis with α-Diazocarbonyl CompoundsAlan Ford†, Hugues Miel§, Aoife Ring†, Catherine N. Slattery†, Anita R. Maguire*†‡, and M. Anthony McKervey*∥View Author Information† ‡ †Department of Chemistry and ‡School of Pharmacy, Analytical and Biological Chemistry Research Facility, Synthesis and Solid State Pharmaceutical Centre, University College Cork, Cork, Ireland§ Almac Discovery Ltd., David Keir Building, Stranmillis Road, Belfast BT9 5AG, United Kingdom∥ Almac Sciences Ltd., Almac House, 20 Seagoe Industrial Estate, Craigavon BT63 5QD, United Kingdom*E-mail: [email protected]*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 18, 9981–10080Publication Date (Web):August 18, 2015Publication History Received26 February 2015Published online18 August 2015Published inissue 23 September 2015https://pubs.acs.org/doi/10.1021/acs.chemrev.5b00121https://doi.org/10.1021/acs.chemrev.5b00121review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views34843Altmetric-Citations1245LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Addition reactions,Catalysts,Insertion reactions,Rearrangement,Stereoselectivity Get e-Alerts

The Chemistry of the Cyclopropyl Group

1995-12-15

Zvi Rappoport

Partial table of contents: Prologue: History of Cyclopropane Derivatives before 1916 (J. Conant). General and Theoretical Aspects of the Cyclopropyl Group (D. Cremer, et al.). Structural Chemistry of Cyclopropane Derivatives … Partial table of contents: Prologue: History of Cyclopropane Derivatives before 1916 (J. Conant). General and Theoretical Aspects of the Cyclopropyl Group (D. Cremer, et al.). Structural Chemistry of Cyclopropane Derivatives (B. Rozsondai). Interrelations in the Thermochemistry of Cyclopropanes (J. Liebman). Cyclopropane Photochemistry (H. Zimmerman). Thermal Stereomutations of Cyclopropanes and Vinylcyclopropanes (J. Baldwin). Metal Catalysed Cyclopropanations (T. Ye & M. McKervey). Cycloproparenes (B. Halton). Spiroannulated Cyclopropanes (K. Lukin & N. Zefirov). Indexes.

Modern catalytic methods for organic synthesis with diazo compounds: from cyclopropanes to ylides

1998-07-01

Michael P. Doyle , M. Anthony McKervey , Ye Tao

Synthesis of Alpha-Diazocarbonyl Compounds. Catalysts for Metal Carbene Transformations. Insertion Reactions. Intermolecular Cyclopropanation and Related Addition Reactions. Intramolecular Cyclopropanation and Related Addition Reactions. Cycloaddition and Substitution Reactions with Aromatic and … Synthesis of Alpha-Diazocarbonyl Compounds. Catalysts for Metal Carbene Transformations. Insertion Reactions. Intermolecular Cyclopropanation and Related Addition Reactions. Intramolecular Cyclopropanation and Related Addition Reactions. Cycloaddition and Substitution Reactions with Aromatic and Heteroaromatic Compounds. Generation and Reactions of Ylides from Diazocarbonyl Compounds. X-H Insertion Reactions of Diazocarbonyl Compounds (X = N,O,S,Se,P, Halogen). The Wolff Rearrangement and Related Reactions. Reactions of Alpha-Diazocarbonyl Compounds with Aldehydes and Ketones. Acid-Promoted Cyclization of Unsaturated and Aromatic Diazo Ketones. Miscellaneous Diazocarbonyl Reactions. Index.

Stereoselective Cyclopropanation Reactions

2003-04-01

H. Lebel , Jean-François Marcoux , Carmela Molinaro +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereoselective Cyclopropanation ReactionsHélène Lebel, Jean-François Marcoux, Carmela Molinaro, and André B. CharetteView Author Information Département de Chimie, Université de Montréal, Montréal, Québec, Canada H3C 3J7 Cite this: … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereoselective Cyclopropanation ReactionsHélène Lebel, Jean-François Marcoux, Carmela Molinaro, and André B. CharetteView Author Information Département de Chimie, Université de Montréal, Montréal, Québec, Canada H3C 3J7 Cite this: Chem. Rev. 2003, 103, 4, 977–1050Publication Date (Web):April 9, 2003Publication History Received30 August 2002Published online9 April 2003Published inissue 1 April 2003https://pubs.acs.org/doi/10.1021/cr010007ehttps://doi.org/10.1021/cr010007eresearch-articleACS PublicationsCopyright © 2003 American Chemical SocietyRequest reuse permissionsArticle Views26779Altmetric-Citations1587LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Cyclopropanation,Hydrocarbons,Molecular structure,Reagents,Stereoselectivity Get e-Alerts

New rules of selectivity: allylic alkylations catalyzed by palladium

1980-11-01

Barry M. Trost

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNew rules of selectivity: allylic alkylations catalyzed by palladiumBarry M. TrostCite this: Acc. Chem. Res. 1980, 13, 11, 385–393Publication Date (Print):November 1, 1980Publication History Published online1 May … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTNew rules of selectivity: allylic alkylations catalyzed by palladiumBarry M. TrostCite this: Acc. Chem. Res. 1980, 13, 11, 385–393Publication Date (Print):November 1, 1980Publication History Published online1 May 2002Published inissue 1 November 1980https://pubs.acs.org/doi/10.1021/ar50155a001https://doi.org/10.1021/ar50155a001research-articleACS PublicationsRequest reuse permissionsArticle Views3223Altmetric-Citations606LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Diazo Compounds and N-Tosylhydrazones: Novel Cross-Coupling Partners in Transition-Metal-Catalyzed Reactions

2012-09-26

Qing Xiao , Yan Zhang , Jianbo Wang

Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, … Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo compounds or N-tosylhydrazones show that these transformations also work with other transition metals, demonstrating the generality of the diazo compounds as new cross-coupling partners in transition-metal-catalyzed coupling reactions.

Catalytic Carbene Insertion into C−H Bonds

2009-09-28

Michael P. Doyle , R. Duffy , Maxim O. Ratnikov +1 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCatalytic Carbene Insertion into C−H BondsMichael P. Doyle*, Richard Duffy, Maxim Ratnikov, and Lei ZhouView Author Information Department of Chemistry and Biochemistry, University of Maryland, College Park, … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCatalytic Carbene Insertion into C−H BondsMichael P. Doyle*, Richard Duffy, Maxim Ratnikov, and Lei ZhouView Author Information Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742* Corresponding author e-mail: [email protected]Cite this: Chem. Rev. 2010, 110, 2, 704–724Publication Date (Web):September 28, 2009Publication History Received2 July 2009Published online28 September 2009Published inissue 10 February 2010https://doi.org/10.1021/cr900239nCopyright © 2009 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views31512Altmetric-Citations1447LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (2 MB) Get e-AlertsSUBJECTS:Carbene compounds,Catalysts,Insertion reactions,Ligands,Metals Get e-Alerts

Bis(imino)pyridines: Surprisingly Reactive Ligands and a Gateway to New Families of Catalysts

2007-05-01

V.C. Gibson , Carl Redshaw , Gregory A. Solan

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBis(imino)pyridines: Surprisingly Reactive Ligands and a Gateway to New Families of CatalystsVernon C. Gibson, Carl Redshaw, and Gregory A. SolanView Author Information Department of Chemistry, Imperial College, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBis(imino)pyridines: Surprisingly Reactive Ligands and a Gateway to New Families of CatalystsVernon C. Gibson, Carl Redshaw, and Gregory A. SolanView Author Information Department of Chemistry, Imperial College, South Kensington Campus, London, SW7 2AZ, United Kingdom, Wolfson Materials and Catalysis Centre, School of Chemical Sciences and Pharmacy, The University of East Anglia, Norwich, NR4 7TJ, United Kingdom, and Department of Chemistry, University of Leicester, University Road, Leicester, LE1 7RH, United Kingdom Cite this: Chem. Rev. 2007, 107, 5, 1745–1776Publication Date (Web):May 9, 2007Publication History Received12 October 2006Published online9 May 2007Published inissue 1 May 2007https://doi.org/10.1021/cr068437yCopyright © 2007 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views8748Altmetric-Citations726LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (880 KB) Get e-AlertsSUBJECTS:Alkyls,Anions,Catalysts,Iron,Ligands Get e-Alerts

Enantioselective Copper-Catalyzed 1,3-Dipolar Cycloadditions

2008-07-10

Levi M. Stanley , Mukund P. Sibi

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnantioselective Copper-Catalyzed 1,3-Dipolar CycloadditionsLevi M. Stanley and Mukund P. Sibi*View Author Information Department of Chemistry and Molecular Biology, North Dakota State University, Fargo, North Dakota, 58105*Email: [email … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnantioselective Copper-Catalyzed 1,3-Dipolar CycloadditionsLevi M. Stanley and Mukund P. Sibi*View Author Information Department of Chemistry and Molecular Biology, North Dakota State University, Fargo, North Dakota, 58105*Email: [email protected].Cite this: Chem. Rev. 2008, 108, 8, 2887–2902Publication Date (Web):July 10, 2008Publication History Received29 January 2008Published online10 July 2008Published inissue 1 August 2008https://pubs.acs.org/doi/10.1021/cr078371mhttps://doi.org/10.1021/cr078371mreview-articleACS PublicationsCopyright © 2008 American Chemical SocietyRequest reuse permissionsArticle Views13634Altmetric-Citations756LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Azomethine,Cyclization,Hydrocarbons,Nitrogen compounds,Stereoselectivity Get e-Alerts

Carbonyl olefination reaction using silyl-substituted organometallic compounds

1968-02-01

Donald J. Peterson

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbonyl olefination reaction using silyl-substituted organometallic compoundsDonald John PetersonCite this: J. Org. Chem. 1968, 33, 2, 780–784Publication Date (Print):February 1, 1968Publication History Published online1 May 2002Published inissue … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbonyl olefination reaction using silyl-substituted organometallic compoundsDonald John PetersonCite this: J. Org. Chem. 1968, 33, 2, 780–784Publication Date (Print):February 1, 1968Publication History Published online1 May 2002Published inissue 1 February 1968https://doi.org/10.1021/jo01266a061RIGHTS & PERMISSIONSArticle Views5599Altmetric-Citations682LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (713 KB) Get e-Alerts Get e-Alerts

Construction of Pyridine Rings by Metal-Mediated [2 + 2 + 2] Cycloaddition

2003-07-23

Jesús A. Varela , Carlos Saá

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTConstruction of Pyridine Rings by Metal-Mediated [2 + 2 + 2] Cycloaddition†Jesús A. Varela and Carlos SaáView Author Information Departamento de Química Orgánica y Unidad Asociada al … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTConstruction of Pyridine Rings by Metal-Mediated [2 + 2 + 2] Cycloaddition†Jesús A. Varela and Carlos SaáView Author Information Departamento de Química Orgánica y Unidad Asociada al CSIC, Facultad de Química, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain Cite this: Chem. Rev. 2003, 103, 9, 3787–3802Publication Date (Web):July 23, 2003Publication History Received20 March 2003Published online23 July 2003Published inissue 1 September 2003https://pubs.acs.org/doi/10.1021/cr030677fhttps://doi.org/10.1021/cr030677fresearch-articleACS PublicationsCopyright © 2003 American Chemical SocietyRequest reuse permissionsArticle Views7518Altmetric-Citations711LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Cyclization,Hydrocarbons,Nitrogen compounds,Pyridines,Substituents Get e-Alerts

Ylide formation from the reaction of carbenes and carbenoids with heteroatom lone pairs

1991-05-01

Albert Padwa , Susan F. Hornbuckle

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTYlide formation from the reaction of carbenes and carbenoids with heteroatom lone pairsAlbert. Padwa and Susan F. HornbuckleCite this: Chem. Rev. 1991, 91, 3, 263–309Publication Date (Print):May … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTYlide formation from the reaction of carbenes and carbenoids with heteroatom lone pairsAlbert. Padwa and Susan F. HornbuckleCite this: Chem. Rev. 1991, 91, 3, 263–309Publication Date (Print):May 1, 1991Publication History Published online1 May 2002Published inissue 1 May 1991https://pubs.acs.org/doi/10.1021/cr00003a001https://doi.org/10.1021/cr00003a001research-articleACS PublicationsRequest reuse permissionsArticle Views5842Altmetric-Citations651LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Asymmetric Ylide Reactions: Epoxidation, Cyclopropanation, Aziridination, Olefination, and Rearrangement

1997-10-01

Anhu Li , Li‐Xin Dai , Varinder K. Aggarwal

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric Ylide Reactions: Epoxidation, Cyclopropanation, Aziridination, Olefination, and Rearrangement†An-Hu Li, Li-Xin Dai, and Varinder K. AggarwalView Author Information Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric Ylide Reactions: Epoxidation, Cyclopropanation, Aziridination, Olefination, and Rearrangement†An-Hu Li, Li-Xin Dai, and Varinder K. AggarwalView Author Information Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China Department of Chemistry, Dainton Building, The University of Sheffield, Sheffield S3 7HF, The United KingdomCite this: Chem. Rev. 1997, 97, 6, 2341–2372Publication Date (Web):October 1, 1997Publication History Received10 March 1997Revised28 May 1997Published online1 October 1997Published inissue 1 October 1997https://pubs.acs.org/doi/10.1021/cr960411rhttps://doi.org/10.1021/cr960411rresearch-articleACS PublicationsCopyright © 1997 American Chemical SocietyRequest reuse permissionsArticle Views12579Altmetric-Citations775LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Cyclopropanation,Organic reactions,Rearrangement,Salts,Sulfides Get e-Alerts

Guiding principles for site selective and stereoselective intermolecular C–H functionalization by donor/acceptor rhodium carbenes

2011-01-01

Huw M. L. Davies , Daniel Morton

This tutorial review presents a description of the controlling elements of intermolecular C–H functionalization by means of C–H insertion by donor/acceptor rhodium carbenes. These rhodium carbenes, readily derived from the … This tutorial review presents a description of the controlling elements of intermolecular C–H functionalization by means of C–H insertion by donor/acceptor rhodium carbenes. These rhodium carbenes, readily derived from the combination of diazo compounds with dirhodium(II) catalysts, are sufficiently reactive to undergo a wide range of C–H insertions. They are also capable of highly selective reactions, controlled by a combination of steric and electronic factors. An overview of the structural factors that influence site selectivity will be given, followed by a description of the exceptional diastereo- and enantioselectivity that can be achieved. Several examples will be shown of how this methodology can be applied to streamline the synthesis of natural products and pharmaceutical targets.

Tosylhydrazones: New Uses for Classic Reagents in Palladium‐Catalyzed Cross‐Coupling and Metal‐Free Reactions

2011-07-11

José Barluenga , Carlos Valdés

Abstract Tosylhydrazones are useful synthetic intermediates that have been used in organic chemistry for almost 60 years. The recent discovery of a palladium‐catalyzed cross‐coupling reaction involving a tosylhydrazone coupling partner … Abstract Tosylhydrazones are useful synthetic intermediates that have been used in organic chemistry for almost 60 years. The recent discovery of a palladium‐catalyzed cross‐coupling reaction involving a tosylhydrazone coupling partner has triggered renewed interest in these reagents. This reaction shows nearly universal generality with regard to the hydrazone and can be employed for the preparation of polysubstituted alkenes. In the course of this research, novel metal‐free CC and CO bond‐forming reactions have been discovered. Since tosylhydrazones are readily prepared from carbonyl compounds, these transformations offer new synthetic opportunities for the unconventional modification of carbonyl compounds. This Minireview discusses all of these new reactions of a classic reagent.

Mechanisms of Catalysis of Nucleophilic Reactions of Carboxylic Acid Derivatives.

1960-02-01

Myron L. Bender

ADVERTISEMENT RETURN TO ISSUEPREVArticleMechanisms of Catalysis of Nucleophilic Reactions of Carboxylic Acid Derivatives.Myron L. BenderCite this: Chem. Rev. 1960, 60, 1, 53–113Publication Date (Print):February 1, 1960Publication History Published online1 May … ADVERTISEMENT RETURN TO ISSUEPREVArticleMechanisms of Catalysis of Nucleophilic Reactions of Carboxylic Acid Derivatives.Myron L. BenderCite this: Chem. Rev. 1960, 60, 1, 53–113Publication Date (Print):February 1, 1960Publication History Published online1 May 2002Published inissue 1 February 1960https://pubs.acs.org/doi/10.1021/cr60203a005https://doi.org/10.1021/cr60203a005research-articleACS PublicationsRequest reuse permissionsArticle Views6812Altmetric-Citations518LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Catalytic methods for metal carbene transformations

1986-10-01

Michael P. Doyle

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic methods for metal carbene transformationsMichael P. DoyleCite this: Chem. Rev. 1986, 86, 5, 919–939Publication Date (Print):October 1, 1986Publication History Published online1 May 2002Published inissue 1 October … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic methods for metal carbene transformationsMichael P. DoyleCite this: Chem. Rev. 1986, 86, 5, 919–939Publication Date (Print):October 1, 1986Publication History Published online1 May 2002Published inissue 1 October 1986https://pubs.acs.org/doi/10.1021/cr00075a013https://doi.org/10.1021/cr00075a013research-articleACS PublicationsRequest reuse permissionsArticle Views6152Altmetric-Citations908LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Organic Synthesis with .alpha.-Diazo Carbonyl Compounds

1994-06-01

Ye Tao , M. Anthony McKervey

ADVERTISEMENT RETURN TO ISSUEPREVArticleOrganic Synthesis with .alpha.-Diazo Carbonyl CompoundsTao Ye and M. Anthony McKerveyCite this: Chem. Rev. 1994, 94, 4, 1091–1160Publication Date (Print):June 1, 1994Publication History Published online1 May 2002Published … ADVERTISEMENT RETURN TO ISSUEPREVArticleOrganic Synthesis with .alpha.-Diazo Carbonyl CompoundsTao Ye and M. Anthony McKerveyCite this: Chem. Rev. 1994, 94, 4, 1091–1160Publication Date (Print):June 1, 1994Publication History Published online1 May 2002Published inissue 1 June 1994https://pubs.acs.org/doi/10.1021/cr00028a010https://doi.org/10.1021/cr00028a010research-articleACS PublicationsRequest reuse permissionsArticle Views17581Altmetric-Citations1352LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Use of cyclopropanes and their derivatives in organic synthesis

1989-01-01

Henry Ν. C. Wong , Moon Yuen Hon , Chun Wah Tse +3 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTUse of cyclopropanes and their derivatives in organic synthesisHenry N. C. Wong, Moon Yuen Hon, Chun Wah Tse, Yu Chi Yip, James Tanko, and Tomas HudlickyCite this: … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTUse of cyclopropanes and their derivatives in organic synthesisHenry N. C. Wong, Moon Yuen Hon, Chun Wah Tse, Yu Chi Yip, James Tanko, and Tomas HudlickyCite this: Chem. Rev. 1989, 89, 1, 165–198Publication Date (Print):January 1, 1989Publication History Published online1 May 2002Published inissue 1 January 1989https://pubs.acs.org/doi/10.1021/cr00091a005https://doi.org/10.1021/cr00091a005research-articleACS PublicationsRequest reuse permissionsArticle Views6382Altmetric-Citations874LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Transition-Metal-Free Coupling Reactions

2014-09-03

Chang‐Liang Sun , Zhang‐Jie Shi

ADVERTISEMENT RETURN TO ISSUEPREVReviewTransition-Metal-Free Coupling ReactionsChang-Liang Sun and Zhang-Jie Shi*View Author Information Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry … ADVERTISEMENT RETURN TO ISSUEPREVReviewTransition-Metal-Free Coupling ReactionsChang-Liang Sun and Zhang-Jie Shi*View Author Information Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Green Chemistry Center, Peking University, 202 Chengfu Road, 098#, Beijing 100871, China State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 200060, China*E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 18, 9219–9280Publication Date (Web):September 3, 2014Publication History Received18 May 2013Published online3 September 2014Published inissue 24 September 2014https://pubs.acs.org/doi/10.1021/cr400274jhttps://doi.org/10.1021/cr400274jreview-articleACS PublicationsCopyright © 2014 American Chemical SocietyRequest reuse permissionsArticle Views34901Altmetric-Citations908LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Aromatic compounds,Cross coupling reaction,Hydrocarbons,Reagents,Substitution reactions Get e-Alerts

Transition-Metal-Catalyzed Addition of Heteroatom−Hydrogen Bonds to Alkynes

2004-04-14

Francisco Alonso , I. P. Beletskaya , Miguel Yus

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition-Metal-Catalyzed Addition of Heteroatom−Hydrogen Bonds to AlkynesFrancisco Alonso, Irina P. Beletskaya, and Miguel YusView Author Information Departamento de Química Orgánica, Facultad de Ciencias and Instituto de Síntesis … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition-Metal-Catalyzed Addition of Heteroatom−Hydrogen Bonds to AlkynesFrancisco Alonso, Irina P. Beletskaya, and Miguel YusView Author Information Departamento de Química Orgánica, Facultad de Ciencias and Instituto de Síntesis Orgánica (ISO), Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain, and Department of Chemistry, Lomonosov Moscow State University, Vorob'evy Gory, 119992 Moscow, Russia Cite this: Chem. Rev. 2004, 104, 6, 3079–3160Publication Date (Web):April 14, 2004Publication History Received23 October 2003Published online14 April 2004Published inissue 1 June 2004https://pubs.acs.org/doi/10.1021/cr0201068https://doi.org/10.1021/cr0201068research-articleACS PublicationsCopyright © 2004 American Chemical SocietyRequest reuse permissionsArticle Views16553Altmetric-Citations1494LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Cyclization,Hydrocarbons,Organic compounds,Organic reactions Get e-Alerts

Bis(oxazolines) as chiral ligands in metal-catalyzed asymmetric reactions. Catalytic, asymmetric cyclopropanation of olefins

1991-01-01

David A. Evans , K. A. Woerpel , Mira M. Hinman +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBis(oxazolines) as chiral ligands in metal-catalyzed asymmetric reactions. Catalytic, asymmetric cyclopropanation of olefinsDavid A. Evans, Keith A. Woerpel, Mira M. Hinman, and Margaret M. FaulCite this: J. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBis(oxazolines) as chiral ligands in metal-catalyzed asymmetric reactions. Catalytic, asymmetric cyclopropanation of olefinsDavid A. Evans, Keith A. Woerpel, Mira M. Hinman, and Margaret M. FaulCite this: J. Am. Chem. Soc. 1991, 113, 2, 726–728Publication Date (Print):January 1, 1991Publication History Published online1 May 2002Published inissue 1 January 1991https://pubs.acs.org/doi/10.1021/ja00002a080https://doi.org/10.1021/ja00002a080research-articleACS PublicationsRequest reuse permissionsArticle Views8688Altmetric-Citations853LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Catalytic Enantioselective C−H Activation by Means of Metal−Carbenoid-Induced C−H Insertion

2003-06-11

Huw M. L. Davies , Rohan E. J. Beckwith

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic Enantioselective C−H Activation by Means of Metal−Carbenoid-Induced C−H InsertionHuw M. L. Davies and Rohan E. J. BeckwithView Author Information Department of Chemistry, State University of New … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic Enantioselective C−H Activation by Means of Metal−Carbenoid-Induced C−H InsertionHuw M. L. Davies and Rohan E. J. BeckwithView Author Information Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000 Cite this: Chem. Rev. 2003, 103, 8, 2861–2904Publication Date (Web):June 11, 2003Publication History Received3 February 2003Published online11 June 2003Published inissue 1 August 2003https://pubs.acs.org/doi/10.1021/cr0200217https://doi.org/10.1021/cr0200217research-articleACS PublicationsCopyright © 2003 American Chemical SocietyRequest reuse permissionsArticle Views25038Altmetric-Citations1498LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Carbene compounds,Catalysts,Chemical reactions,Stereoselectivity,Substituents Get e-Alerts

Transition-Metal-Catalyzed Reactions in Heterocyclic Synthesis

2004-02-21

Itaru Nakamura , Yoshinori Yamamoto

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition-Metal-Catalyzed Reactions in Heterocyclic SynthesisItaru Nakamura and Yoshinori YamamotoView Author Information Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan Cite this: Chem. Rev. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition-Metal-Catalyzed Reactions in Heterocyclic SynthesisItaru Nakamura and Yoshinori YamamotoView Author Information Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan Cite this: Chem. Rev. 2004, 104, 5, 2127–2198Publication Date (Web):February 21, 2004Publication History Received12 August 2003Published online21 February 2004Published inissue 1 May 2004https://pubs.acs.org/doi/10.1021/cr020095ihttps://doi.org/10.1021/cr020095iresearch-articleACS PublicationsCopyright © 2004 American Chemical SocietyRequest reuse permissionsArticle Views17913Altmetric-Citations1421LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Cyclization,Heterocyclic compounds,Hydrocarbons,Inorganic carbon compounds Get e-Alerts

Synthesis of cyclopropane containing natural products

2001-10-01

William A. Donaldson

View PDF Chat

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

2008-01-01

Huw M. L. Davies , James R. Manning

View PDF Chat

Methanolysis of Dimethyl (1-Diazo-2-oxopropyl) Phosphonate: Generation of Dimethyl (Diazomethyl) Phosphonate and Reaction with Carbonyl Compounds

1989-02-01

Susumu Ohira

Abstract Dimethyl (1-diazo-2-oxopropyl) phosphonate (3) was transformed to dimethyl (diazomethyl)—phosphonate (4), which was used for the synthesis of enol ether or alkyne without isolation. Abstract Dimethyl (1-diazo-2-oxopropyl) phosphonate (3) was transformed to dimethyl (diazomethyl)—phosphonate (4), which was used for the synthesis of enol ether or alkyne without isolation.

Large-Scale Applications of Transition Metal-Catalyzed Couplings for the Synthesis of Pharmaceuticals

2011-03-09

Javier Magano , Joshua R. Dunetz

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTLarge-Scale Applications of Transition Metal-Catalyzed Couplings for the Synthesis of PharmaceuticalsJavier Magano* and Joshua R. Dunetz*View Author Information Research API, Pharmaceutical Sciences, Pfizer, Inc., Eastern Point Road, … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTLarge-Scale Applications of Transition Metal-Catalyzed Couplings for the Synthesis of PharmaceuticalsJavier Magano* and Joshua R. Dunetz*View Author Information Research API, Pharmaceutical Sciences, Pfizer, Inc., Eastern Point Road, Groton, Connecticut 06340, United States*Phone: 860-686-9021 (Magano); 860-715-6752 (Dunetz). Fax: 860-715-4978. E-mail: [email protected]; [email protected]Cite this: Chem. Rev. 2011, 111, 3, 2177–2250Publication Date (Web):March 9, 2011Publication History Received15 October 2010Published online9 March 2011Published inissue 9 March 2011https://pubs.acs.org/doi/10.1021/cr100346ghttps://doi.org/10.1021/cr100346greview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views27721Altmetric-Citations1495LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Anions,Catalysts,Coupling reactions,Mixtures,Palladium Get e-Alerts

Olefin Cyclopropanation via Carbene Transfer Catalyzed by Engineered Cytochrome P450 Enzymes

2012-12-21

Pedro S. Coelho , Eric M. Brustad , Arvind Kannan +1 more

Transition metal-catalyzed transfers of carbenes, nitrenes, and oxenes are powerful methods for functionalizing C=C and C-H bonds. Nature has evolved a diverse toolbox for oxene transfers, as exemplified by the … Transition metal-catalyzed transfers of carbenes, nitrenes, and oxenes are powerful methods for functionalizing C=C and C-H bonds. Nature has evolved a diverse toolbox for oxene transfers, as exemplified by the myriad monooxygenation reactions catalyzed by cytochrome P450 enzymes. The isoelectronic carbene transfer to olefins, a widely used C-C bond-forming reaction in organic synthesis, has no biological counterpart. Here we report engineered variants of cytochrome P450(BM3) that catalyze highly diastereo- and enantioselective cyclopropanation of styrenes from diazoester reagents via putative carbene transfer. This work highlights the capacity to adapt existing enzymes for the catalysis of synthetically important reactions not previously observed in nature.

View PDF Chat

A NEW SYNTHESIS OF CYCLOPROPANES FROM OLEFINS

1958-10-01

Howard E. Simmons , Ronald D. Smith

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA NEW SYNTHESIS OF CYCLOPROPANES FROM OLEFINSHoward E. Simmons and Ronald D. SmithCite this: J. Am. Chem. Soc. 1958, 80, 19, 5323–5324Publication Date (Print):October 1, 1958Publication History … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA NEW SYNTHESIS OF CYCLOPROPANES FROM OLEFINSHoward E. Simmons and Ronald D. SmithCite this: J. Am. Chem. Soc. 1958, 80, 19, 5323–5324Publication Date (Print):October 1, 1958Publication History Published online1 May 2002Published inissue 1 October 1958https://pubs.acs.org/doi/10.1021/ja01552a080https://doi.org/10.1021/ja01552a080research-articleACS PublicationsRequest reuse permissionsArticle Views4738Altmetric-Citations551LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Cascade Processes of Metallo Carbenoids

1996-01-01

Albert Padwa , M. David Weingarten

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCascade Processes of Metallo CarbenoidsAlbert Padwa and M. David WeingartenView Author Information Department of Chemistry, Emory University, Atlanta, Georgia 30322 Cite this: Chem. Rev. 1996, 96, 1, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCascade Processes of Metallo CarbenoidsAlbert Padwa and M. David WeingartenView Author Information Department of Chemistry, Emory University, Atlanta, Georgia 30322 Cite this: Chem. Rev. 1996, 96, 1, 223–270Publication Date (Web):February 1, 1996Publication History Received12 June 1995Revised15 September 1995Published online1 February 1996Published inissue 1 January 1996https://pubs.acs.org/doi/10.1021/cr950022hhttps://doi.org/10.1021/cr950022hresearch-articleACS PublicationsCopyright © 1996 American Chemical SocietyRequest reuse permissionsArticle Views12173Altmetric-Citations780LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Carbonyls,Cyclization,Hydrocarbons,Ketones,Molecular structure Get e-Alerts

Transition Metal Chemistry of Cyclopropenes and Cyclopropanes

2007-07-01

Michael Rubin , Marina Rubina , Vladimir Gevorgyan

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition Metal Chemistry of Cyclopropenes and CyclopropanesMichael Rubin, Marina Rubina, and Vladimir GevorgyanView Author Information Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition Metal Chemistry of Cyclopropenes and CyclopropanesMichael Rubin, Marina Rubina, and Vladimir GevorgyanView Author Information Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, and Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607 Cite this: Chem. Rev. 2007, 107, 7, 3117–3179Publication Date (Web):July 11, 2007Publication History Received10 October 2006Published online11 July 2007Published inissue 1 July 2007https://pubs.acs.org/doi/10.1021/cr050988lhttps://doi.org/10.1021/cr050988lresearch-articleACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views15842Altmetric-Citations1126LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Addition reactions,Catalysts,Cross coupling reaction,Cyclization,Hydrocarbons Get e-Alerts

Intramolecular donor–acceptor cyclopropane ring-opening cyclizations

2013-11-21

Marchello A. Cavitt , Lien H. Phun , Stefan France

Cyclization reactions of donor-acceptor (D-A) cyclopropanes are recognized as versatile methods for construction of carbocyclic and heterocyclic scaffolds. In the literature, many examples of these polarized cyclopropanes' reactivity with nucleophiles, … Cyclization reactions of donor-acceptor (D-A) cyclopropanes are recognized as versatile methods for construction of carbocyclic and heterocyclic scaffolds. In the literature, many examples of these polarized cyclopropanes' reactivity with nucleophiles, electrophiles, and radicals are prevalent. Although intermolecular reactivity of donor-acceptor cyclopropanes is widely reported, reviews that center on their intramolecular chemistry are rare. Thereupon, this tutorial review focalizes on new intramolecular transformations of donor-acceptor cyclopropanes for cycloisomerizations, formal cycloadditions, umpolung reactions, rearrangements and ring-opening lactonizations/lactamizations from 2009 to 2013. Furthermore, the role of D-A acceptor cyclopropanes as reactive subunits in natural product synthesis is underscored.

Atomökonomische Synthesen – eine Herausforderung in der Organischen Chemie: die Homogenkatalyse als wegweisende Methode

1995-02-07

Barry M. Trost

Abstract Die Effizienz der Synthese komplexer organischer Verbindungen zu steigern gehört zu den reizvollsten Aufgaben für Synthesechemiker. Als erster Schritt hierzu ist die Entwicklung einer großen Zahl einfacher Additionsreaktionen und … Abstract Die Effizienz der Synthese komplexer organischer Verbindungen zu steigern gehört zu den reizvollsten Aufgaben für Synthesechemiker. Als erster Schritt hierzu ist die Entwicklung einer großen Zahl einfacher Additionsreaktionen und die Minimierung von Abfallprodukten erforderlich. Im Brennpunkt solcher Forschungen stehen Übergangsmetallkomplexe, die durch Änderung des Metalls und/oder der Liganden sowohl elektronisch als auch sterisch an die jeweiligen Erfordernisse exakt angepaßt werden können. Mit Ausnahme der katalytischen Hydrierung sind solche Methoden in komplexen Synthesen selten angewendet worden und waren für CC‐Verknüpfungen bis zur Entwicklung der Kreuzkupplungen nahezu unbekannt. Übergangsmetallkomplexe können an einer Vielzahl von CC‐Bindungsbildungen beteiligt sein, die für den Aufbau der Grundgerüste organischer Verbindungen von Bedeutung sind. Ihre Fähigkeit, sich in CH‐Bindungen einzuschieben, ist Grundlage zahlreicher Additionsreaktionen an relativ unpolare π‐Elektronensysteme. Sie ermöglichen nicht nur selektivere Reaktionen, sondern auch unkatalysiert nicht bekannte. Auf der Fähigkeit dieser Komplexe, π‐Elektronensysteme zu präorganisieren, beruhen sowohl einfache Additionen, die im allgemeinen mit anschließenden Wasserstoffverschiebungen einhergehen, als auch Cycloadditionen. Die Bildung „reaktiver”︁ Zwischenstufen unter milden Bedingungen stellt außerdem neue Arten von CC‐Verknüpfungen in Aussicht. Auch wenn hier eine Vielzahl erfolgreicher neuer Reaktionen vorgestellt wird, sind die Möglichkeiten für neue Entdeckungen enorm und bei weitem noch nicht ausgeschöpft.

Intramolecular Dipolar Cycloaddition Reactions of Azomethine Ylides

2005-06-25

Iain Coldham , Richard Hufton

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIntramolecular Dipolar Cycloaddition Reactions of Azomethine YlidesIain Coldham and Richard HuftonView Author Information Department of Chemistry, University of Sheffield, Sheffield S3 7HF, U.K., and Tripos Discovery Research … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIntramolecular Dipolar Cycloaddition Reactions of Azomethine YlidesIain Coldham and Richard HuftonView Author Information Department of Chemistry, University of Sheffield, Sheffield S3 7HF, U.K., and Tripos Discovery Research Ltd., Bude-Stratton Business Park, Bude EX23 8LY, U.K. Cite this: Chem. Rev. 2005, 105, 7, 2765–2810Publication Date (Web):June 25, 2005Publication History Received13 September 2004Published online25 June 2005Published inissue 1 July 2005https://pubs.acs.org/doi/10.1021/cr040004chttps://doi.org/10.1021/cr040004cresearch-articleACS PublicationsCopyright © 2005 American Chemical SocietyRequest reuse permissionsArticle Views14271Altmetric-Citations936LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Addition reactions,Azomethine,Cyclization,Hydrocarbons,Molecular structure Get e-Alerts

Recent studies on the reactions of α-diazocarbonyl compounds

2008-04-25

Zhenhua Zhang , Jianbo Wang

Donor−Acceptor-Substituted Cyclopropane Derivatives and Their Application in Organic Synthesis

2003-02-21

Hans‐Ulrich Reißig , Reinhold Zimmer

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDonor−Acceptor-Substituted Cyclopropane Derivatives and Their Application in Organic Synthesis†Hans-Ulrich Reissig and Reinhold ZimmerView Author Information Institut für Chemie−Organische Chemie, Freie Universität Berlin, Takustrasse 3, D-14195 Berlin, Germany … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDonor−Acceptor-Substituted Cyclopropane Derivatives and Their Application in Organic Synthesis†Hans-Ulrich Reissig and Reinhold ZimmerView Author Information Institut für Chemie−Organische Chemie, Freie Universität Berlin, Takustrasse 3, D-14195 Berlin, Germany Cite this: Chem. Rev. 2003, 103, 4, 1151–1196Publication Date (Web):February 21, 2003Publication History Received15 July 2002Published online21 February 2003Published inissue 1 April 2003https://pubs.acs.org/doi/10.1021/cr010016nhttps://doi.org/10.1021/cr010016nresearch-articleACS PublicationsCopyright © 2003 American Chemical SocietyRequest reuse permissionsArticle Views14491Altmetric-Citations1372LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Crystal cleavage,Cyclopropanation,Hydrocarbons,Organic compounds,Reaction products Get e-Alerts

Heterocycles from cyclopropanes: applications in natural product synthesis

2009-01-01

Cheryl A. Carson , Michael A. Kerr

The construction of heterocyclic compounds from activated cyclopropane derivatives offers an alternative strategy for the preparation of molecules that may be of interest from a structural or biological standpoint. Several … The construction of heterocyclic compounds from activated cyclopropane derivatives offers an alternative strategy for the preparation of molecules that may be of interest from a structural or biological standpoint. Several newly developed methods provide access to densely functionalized heterocycles in a manner that can be considered useful for both diversity- and target-oriented synthetic approaches. This tutorial review focuses on the latter, describing recent developments and applications of cyclopropane ring-expansion reactions in natural product synthesis.

A New Golden Age for Donor–Acceptor Cyclopropanes

2014-04-25

Tobias F. Schneider , Johannes Kaschel , Daniel B. Werz

Abstract The effective use of ring strain has been applied to considerable advantage for the construction of complex systems. The focus here is directed towards cyclopropanes as building blocks for … Abstract The effective use of ring strain has been applied to considerable advantage for the construction of complex systems. The focus here is directed towards cyclopropanes as building blocks for organic synthesis. Although thermodynamics should take the side of synthetic chemists, only a specific substitution pattern at the cyclopropane ring allows for particularly mild, efficient, and selective transformations. The required decrease in the activation barrier is achieved by the combined effects of vicinal electron‐donating and electron‐accepting moieties. This Review highlights the appropriate tools for successfully employing donor–acceptor cyclopropanes in ring‐opening reactions, cycloadditions, and rearrangements.

View PDF Chat

Stronger Brønsted Acids: Recent Progress

2015-07-16

Takahiko Akiyama , Keiji Mori

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTStronger Brønsted Acids: Recent ProgressTakahiko Akiyama*† and Keiji Mori†‡View Author Information† Department of Chemistry, Faculty of Science, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo 171-8588, Japan‡ Department of … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTStronger Brønsted Acids: Recent ProgressTakahiko Akiyama*† and Keiji Mori†‡View Author Information† Department of Chemistry, Faculty of Science, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo 171-8588, Japan‡ Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho Koganei, Tokyo 184-8588, Japan*Fax: +81-3-5992-1029. E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 17, 9277–9306Publication Date (Web):July 16, 2015Publication History Received22 January 2015Published online16 July 2015Published inissue 9 September 2015https://pubs.acs.org/doi/10.1021/acs.chemrev.5b00041https://doi.org/10.1021/acs.chemrev.5b00041review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views18646Altmetric-Citations580LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Addition reactions,Aldol reactions,Brønsted acid,Catalysts,Reaction products Get e-Alerts

Recent Advances of Catalytic Asymmetric 1,3-Dipolar Cycloadditions

2015-05-11

Takuya Hashimoto , Keiji Maruoka

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTADDITION / CORRECTIONThis article has been corrected. View the notice.Recent Advances of Catalytic Asymmetric 1,3-Dipolar CycloadditionsTakuya Hashimoto* and Keiji Maruoka*View Author Information Department of Chemistry, Graduate School … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTADDITION / CORRECTIONThis article has been corrected. View the notice.Recent Advances of Catalytic Asymmetric 1,3-Dipolar CycloadditionsTakuya Hashimoto* and Keiji Maruoka*View Author Information Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan*E-mail: [email protected]*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 11, 5366–5412Publication Date (Web):May 11, 2015Publication History Received29 December 2014Published online11 May 2015Published inissue 10 June 2015https://pubs.acs.org/doi/10.1021/cr5007182https://doi.org/10.1021/cr5007182review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views22275Altmetric-Citations824LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Azomethine,Catalysts,Cyclization,Nitrogen compounds,Stereoselectivity Get e-Alerts

A New Synthesis of Cyclopropanes1

1959-08-01

Howard E. Simmons , Ronald D. Smith

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA New Synthesis of Cyclopropanes1Howard E. Simmons and Ronald D. SmithCite this: J. Am. Chem. Soc. 1959, 81, 16, 4256–4264Publication Date (Print):August 1, 1959Publication History Published online1 … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA New Synthesis of Cyclopropanes1Howard E. Simmons and Ronald D. SmithCite this: J. Am. Chem. Soc. 1959, 81, 16, 4256–4264Publication Date (Print):August 1, 1959Publication History Published online1 May 2002Published inissue 1 August 1959https://doi.org/10.1021/ja01525a036RIGHTS & PERMISSIONSArticle Views4082Altmetric-Citations608LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

Transition-Metal-Catalyzed Enantioselective Heteroatom–Hydrogen Bond Insertion Reactions

2012-05-31

Shou‐Fei Zhu , Qi‐Lin Zhou

Carbon-heteroatom bonds (C-X) are ubiquitous and are among the most reactive components of organic compounds. Therefore investigations of the construction of C-X bonds are fundamental and vibrant fields in organic … Carbon-heteroatom bonds (C-X) are ubiquitous and are among the most reactive components of organic compounds. Therefore investigations of the construction of C-X bonds are fundamental and vibrant fields in organic chemistry. Transition-metal-catalyzed heteroatom-hydrogen bond (X-H) insertions via a metal carbene or carbenoid intermediate represent one of the most efficient approaches to form C-X bonds. Because of the availability of substrates, neutral and mild reaction conditions, and high reactivity of these transformations, researchers have widely applied transition-metal-catalyzed X-H insertions in organic synthesis. Researchers have developed a variety of rhodium-catalyzed asymmetric C-H insertion reactions with high to excellent enantioselectivities for a wide range of substrates. However, at the time that we launched our research, very few highly enantioselective X-H insertions had been documented primarily because of a lack of efficient chiral catalysts and indistinct insertion mechanisms. In this Account, we describe our recent studies of copper- and iron-catalyzed asymmetric X-H insertion reactions by using chiral spiro-bisoxazoline and diimine ligands. The copper complexes of chiral spiro-bisoxazoline ligands proved to be highly enantioselective catalysts for N-H insertions of α-diazoesters into anilines, O-H insertions of α-diazoesters into phenols and water, O-H insertions of α-diazophosphonates into alcohols, and S-H insertions of α-diazoesters into mercaptans. The iron complexes of chiral spiro-bisoxazoline ligands afforded the O-H insertion of α-diazoesters into alcohols and water with unprecedented enantioselectivities. The copper complexes of chiral spiro-diimine ligands exhibited excellent reactivity and enantioselectivity in the Si-H insertion of α-diazoacetates into a wide range of silanes. These transition-metal-catalyzed X-H insertions have many potential applications in organic synthesis because the insertion products, including chiral α-aminoesters, α-hydroxyesters, α-hydroxyphosphonates, α-mercaptoesters, and α-silyl esters, are important building blocks for the synthesis of biologically active compounds. The electronic properties of α-diazoesters and anilines markedly affected the enantioselectivity of N-H insertion reaction, which supports a stepwise ylide insertion mechanism. A novel binuclear spiro copper complex was isolated and fully characterized using X-ray diffraction analysis and ESI-MS analysis. The positive nonlinear effect indicated that binuclear copper complexes were the catalytically active species. The 14-electron copper centers, trans coordination model, perfect C(2)-symmetric chiral pocket, and Cu-Cu interaction facilitate the performance of the chiral spiro catalysts in X-H insertion reactions.

The “Cyclopropyl Fragment” is a Versatile Player that Frequently Appears in Preclinical/Clinical Drug Molecules

2016-06-14

Tanaji T. Talele

Recently, there has been an increasing use of the cyclopropyl ring in drug development to transition drug candidates from the preclinical to clinical stage. Important features of the cyclopropane ring … Recently, there has been an increasing use of the cyclopropyl ring in drug development to transition drug candidates from the preclinical to clinical stage. Important features of the cyclopropane ring are, the (1) coplanarity of the three carbon atoms, (2) relatively shorter (1.51 Å) C-C bonds, (3) enhanced π-character of C-C bonds, and (4) C-H bonds are shorter and stronger than those in alkanes. The present review will focus on the contributions that a cyclopropyl ring makes to the properties of drugs containing it. Consequently, the cyclopropyl ring addresses multiple roadblocks that can occur during drug discovery such as (a) enhancing potency, (b) reducing off-target effects,

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

2017-07-17

Fabian Schwizer , Yasunori Okamoto , Tillmann Heinisch +7 more

The incorporation of a synthetic, catalytically competent metallocofactor into a protein scaffold to generate an artificial metalloenzyme (ArM) has been explored since the late 1970's. Progress in the ensuing years … The incorporation of a synthetic, catalytically competent metallocofactor into a protein scaffold to generate an artificial metalloenzyme (ArM) has been explored since the late 1970's. Progress in the ensuing years was limited by the tools available for both organometallic synthesis and protein engineering. Advances in both of these areas, combined with increased appreciation of the potential benefits of combining attractive features of both homogeneous catalysis and enzymatic catalysis, led to a resurgence of interest in ArMs starting in the early 2000's. Perhaps the most intriguing of potential ArM properties is their ability to endow homogeneous catalysts with a genetic memory. Indeed, incorporating a homogeneous catalyst into a genetically encoded scaffold offers the opportunity to improve ArM performance by directed evolution. This capability could, in turn, lead to improvements in ArM efficiency similar to those obtained for natural enzymes, providing systems suitable for practical applications and greater insight into the role of second coordination sphere interactions in organometallic catalysis. Since its renaissance in the early 2000's, different aspects of artificial metalloenzymes have been extensively reviewed and highlighted. Our intent is to provide a comprehensive overview of all work in the field up to December 2016, organized according to reaction class. Because of the wide range of non-natural reactions catalyzed by ArMs, this was done using a functional-group transformation classification. The review begins with a summary of the proteins and the anchoring strategies used to date for the creation of ArMs, followed by a historical perspective. Then follows a summary of the reactions catalyzed by ArMs and a concluding critical outlook. This analysis allows for comparison of similar reactions catalyzed by ArMs constructed using different metallocofactor anchoring strategies, cofactors, protein scaffolds, and mutagenesis strategies. These data will be used to construct a searchable Web site on ArMs that will be updated regularly by the authors.

View PDF Chat

Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

2017-11-01

Ying Xia , Di Qiu , Jianbo Wang

Transition-metal-catalyzed cross-coupling reactions have been well-established as indispensable tools in modern organic synthesis. One of the major research goals in cross-coupling area is expanding the scope of the coupling partners. … Transition-metal-catalyzed cross-coupling reactions have been well-established as indispensable tools in modern organic synthesis. One of the major research goals in cross-coupling area is expanding the scope of the coupling partners. In the past decade, diazo compounds (or their precursors N-tosylhydrazones) have emerged as nucleophilic cross-coupling partners in C-C single bond or C═C double bond formations in transition-metal-catalyzed reactions. This type of coupling reaction involves the following general steps. First, the organometallic species is generated by various processes, including oxidative addition, transmetalation, cyclization, C-C bond cleavage, and C-H bond activation. Subsequently, the organometallic species reacts with the diazo substrate to generate metal carbene intermediate, which undergoes rapid migratory insertion to form a C-C bond. The new organometallic species generated from migratory insertion may undergo various transformations. This type of carbene-based coupling has proven to be general: various transition metals including Pd, Cu, Rh, Ni, Co, and Ir are effective catalysts; the scope of the reaction has also been extended to substrates other than diazo compounds; and various cascade processes have also been devised based on the carbene migratory insertion. This review will summarize the achievements made in this field since 2001.

Recent advances in donor–acceptor (DA) cyclopropanes

2004-12-03

Ming Yu , Brian L. Pagenkopf

Asymmetric 1,3-dipolar cycloadditions

2007-01-17

Hélène Pellissier

Recent Advances in Asymmetric Catalytic Metal Carbene Transformations

1998-03-10

Michael P. Doyle , David C. Forbes

ADVERTISEMENT RETURN TO ISSUEPREVArticleRecent Advances in Asymmetric Catalytic Metal Carbene TransformationsMichael P. Doyle and David C. ForbesView Author Information Department of Chemistry, University of Arizona, Tucson, Arizona 85721 Cite this: … ADVERTISEMENT RETURN TO ISSUEPREVArticleRecent Advances in Asymmetric Catalytic Metal Carbene TransformationsMichael P. Doyle and David C. ForbesView Author Information Department of Chemistry, University of Arizona, Tucson, Arizona 85721 Cite this: Chem. Rev. 1998, 98, 2, 911–936Publication Date (Web):March 10, 1998Publication History Received8 November 1997Revised20 January 1998Published online10 March 1998Published inissue 1 April 1998https://doi.org/10.1021/cr940066aCopyright © 1998 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views9506Altmetric-Citations1108LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (1 MB) Get e-AlertsSUBJECTS:Carbene compounds,Catalysts,Cyclopropanation,Metals,Stereoselectivity Get e-Alerts

An Improved One-pot Procedure for the Synthesis of Alkynes from Aldehydes

1996-06-01

S. Müller , Bernd Liepold , Gerald J. Roth +1 more

The transformation of aldehydes to terminal alkynes can be achieved with the reagent dimethyl-1-diazo-2-oxopropylphosphonate 2. The one-pot procedure allows the isolation of the products under very mild conditions in good … The transformation of aldehydes to terminal alkynes can be achieved with the reagent dimethyl-1-diazo-2-oxopropylphosphonate 2. The one-pot procedure allows the isolation of the products under very mild conditions in good to excellent yields without requiring low temperatures or inert gas techniques and avoiding the use of strong bases.

Site-Selective α-Alkoxylation of Iodonium Ylides with Alcohols via Ruthenium Catalysis

2025-06-25

Sijia Shi , Yaxi Liu , Tian Cao +2 more | Organic Letters

Herein, we report an efficient ruthenium-catalyzed α-alkoxylation of structurally diverse iodonium ylides with a wide range of primary, secondary, and tertiary alcohols under mild conditions. This strategy provides a versatile … Herein, we report an efficient ruthenium-catalyzed α-alkoxylation of structurally diverse iodonium ylides with a wide range of primary, secondary, and tertiary alcohols under mild conditions. This strategy provides a versatile platform for the synthesis of diverse 3-alkoxylated 4-hydroxycoumarins and related analogues. The reaction exhibits high site-selectivity, a wide substrate scope, good functional group tolerance, and scale-up synthesis. Additionally, this work not only expands the application scope of hypervalent iodine reagents but also offers a practical and safer alternative to diazo compounds for C-O bond formation while broadening substrate scope.

Cover Feature: Copper(I)‐Catalyzed Acid‐Controlled Divergent Radical Cyclization of 1,6‐Enynes to Access 1‐Indanones and 1H‐Cyclopropa[b] Naphthalene‐2,7‐diones

2025-06-23

E. Jamshidi , Saideh Rajai‐Daryasarei , Robert Stranger +3 more | Chemistry - A European Journal

Photocatalytic Diazo‐Transfer from Hypervalent Iodine Diazo Reagents to Azocarboxylates: Divergent Access to 1H‐Diazirines and 1H‐Tetrazoles

2025-06-23

Jalaj Kumar Pathak , Oj Shikhar Srivastava , Ruchir Kant +1 more | Advanced Synthesis & Catalysis

The diazo‐group transfer from hypervalent iodine diazo reagents to azocarboxylates under photocatalytic conditions is reported. The subsequent intramolecular decarboxylative cyclization leads to the divergent access to 1H ‐diazirines and 1H … The diazo‐group transfer from hypervalent iodine diazo reagents to azocarboxylates under photocatalytic conditions is reported. The subsequent intramolecular decarboxylative cyclization leads to the divergent access to 1H ‐diazirines and 1H ‐tetrazoles depending upon the substituents in the azo‐substrate. The control experiments suggest that the diazo‐group transfer may take place through photocatalytically generated diazomethyl radical intermediate or through electrophilic diazomethylation of azocarboxylate radical anion.

Ligand‐Controlled Chemoselectivity in the Rhodium‐Catalyzed Synthesis of Pentafulvenes via (2+2+1) Alkyne Cyclotrimerization

2025-06-23

Ricardo Castarlenas , Belinda Español-Sánchez , Jesús Moradell +4 more | Angewandte Chemie

The synthesis of pentafulvenes with varied substituents has been efficiently achieved using novel rhodium‐based catalysts via (2+2+1) alkyne cyclotrimerization. A rational design of the catalyst structure, including pyridonato, NHC and … The synthesis of pentafulvenes with varied substituents has been efficiently achieved using novel rhodium‐based catalysts via (2+2+1) alkyne cyclotrimerization. A rational design of the catalyst structure, including pyridonato, NHC and CO ligands, ensure the alkyne chemoselectivity and prevents the formation of robust rhodium‐fulvene species. Furthermore, the judicious choice of acidity and steric properties of different alkynes enables the preparation of cross‐coupled fulvene derivatives. Stoichiometric and deuteration experiments, as well as DFT calculations, shed light on the reaction mechanism, showing that it includes an initial alkyne deprotonation, two successive alkyne insertions, cyclization, and protonolysis, the first insertion being the rate‐determining step.

Ligand‐Controlled Chemoselectivity in the Rhodium‐Catalyzed Synthesis of Pentafulvenes via (2+2+1) Alkyne Cyclotrimerization

2025-06-23

Ricardo Castarlenas , Belinda Español-Sánchez , Jesús Moradell +4 more | Angewandte Chemie International Edition

The synthesis of pentafulvenes with varied substituents has been efficiently achieved using novel rhodium-based catalysts via (2+2+1) alkyne cyclotrimerization. A rational design of the catalyst structure, including pyridonato, NHC and … The synthesis of pentafulvenes with varied substituents has been efficiently achieved using novel rhodium-based catalysts via (2+2+1) alkyne cyclotrimerization. A rational design of the catalyst structure, including pyridonato, NHC and CO ligands, ensure the alkyne chemoselectivity and prevents the formation of robust rhodium-fulvene species. Furthermore, the judicious choice of acidity and steric properties of different alkynes enables the preparation of cross-coupled fulvene derivatives. Stoichiometric and deuteration experiments, as well as DFT calculations, shed light on the reaction mechanism, showing that it includes an initial alkyne deprotonation, two successive alkyne insertions, cyclization, and protonolysis, the first insertion being the rate-determining step.

Accessing Cyclopropenes and Oxazoles from α-Diazoesters under Cobalt Metalloradical Catalysis

2025-06-23

| Synfacts

Copper-Catalyzed Asymmetric Rearrangement of Carbonyl-Substituted Cyclopropanes to Dihydrofurans

2025-06-23

| Synfacts

Stereodivergent Synthesis of Cyanocyclopropanes via Asymmetric Nitrogen Insertion

2025-06-23

| Synfacts

Chiral Brønsted Base Catalyzed (3+2) Annulation of Cyclopropanes with Nitrosoarenes

2025-06-23

| Synfacts

Vinylarylcyclopropanes (VACPs): All-Carbon Dipole Precursors for Controlling Linear Regioselectivity in Cycloaddition Reactions

2025-06-20

Na Lin , Juntao Chen , Yang‐Zi Liu +1 more | ACS Catalysis

Organocatalytic Enantioselective Nitro-Vinylcyclopropane-Cyclopentene Rearrangement; Expanding the Reactivity of Donor-Acceptor Cyclopropanes

2025-06-20

Lorena García , Luisa Carrillo , Efraím Reyes +3 more | Synthesis

Abstract The catalytic enantioselective rearrangement of nitro-vinylcyclopropylacetaldehydes has been studied using chiral secondary amines as catalysts. The reaction proceeds through the in situ generation of a donor-acceptor cyclopropane which rearranges … Abstract The catalytic enantioselective rearrangement of nitro-vinylcyclopropylacetaldehydes has been studied using chiral secondary amines as catalysts. The reaction proceeds through the in situ generation of a donor-acceptor cyclopropane which rearranges to the corresponding cyclopentene through an open conjugated iminium/unsaturated nitronate intermediate where the stereochemistry of the starting cyclopropane is lost. This intermediate undergoes intramolecular Michael reaction in which the asymmetric induction provided by the catalyst allows the preparation of substituted nitrocyclopentenes in good yields and with high stereocontrol. The obtained 2-nitrocyclopentenylacetaldehydes have been transformed into valuable chiral cyclopentenones through Nef reaction with complete retention of the stereochemical information.

Divergent Asymmetric Synthesis of Bonnadiene and ent‐Polytrichastrene B

2025-06-18

Hui Wang , Lihua Wei , Jiayu Huang +5 more | Angewandte Chemie International Edition

We report herein the first asymmetric total synthesis of bonnadiene and ent‐polytrichastrene B, two diterpenoids that share a common spirotricyclic skeleton. Notably, ent‐polytrichastrene B also features a highly strained, sterically … We report herein the first asymmetric total synthesis of bonnadiene and ent‐polytrichastrene B, two diterpenoids that share a common spirotricyclic skeleton. Notably, ent‐polytrichastrene B also features a highly strained, sterically congested tetrasubstituted cyclopropane moiety, presenting significant synthetic challenges in both its construction and stereochemical control. The synthesis features: (1) Palladium‐catalyzed enantioselective redox‐relay Heck alkenylation between electron‐withdrawing alkenyl triflate and primary alkenol to form the stereocenter at C7; (2) diastereoselective intramolecular [5+2] cycloaddition to rapidly assemble the unique [6,7,5] spirotricyclic skeleton; (3) sequential installation of the requisite alkyl groups and alkenes present in the targeted molecule by leveraging the functionalities positioned on the tricycle; (4) Fe‐catalyzed hydrogen atom transfer (HAT)‐initiated hydrogenation to stereospecifically reduce the tetrasubstituted Δ10,11 olefin and install the contiguous stereocenters; (5) Fe‐mediated HAT‐initiated 3‐exo‐trig radical cyclization to rapidly forge the tetrasubstituted cyclopropane ring with excellent stereoselectivity.

Divergent Asymmetric Synthesis of Bonnadiene and ent‐Polytrichastrene B

2025-06-18

Hui Wang , Lihua Wei , Jiayu Huang +5 more | Angewandte Chemie

Selective Functionalization of Benzene Ring via Carbene Initiated [4,5]‐Rearrangement

2025-06-17

Jiarong Shi , Xuerong Wang , Chuang Mei +4 more | Angewandte Chemie

The extreme similarity in electronic and steric reactivity among the C‐H bonds present on alkyl‐substituted aromatic rings presents a formidable challenge when it comes to achieving high selectivity during the … The extreme similarity in electronic and steric reactivity among the C‐H bonds present on alkyl‐substituted aromatic rings presents a formidable challenge when it comes to achieving high selectivity during the para‐selective functionalization of these bonds. This article presents a unique study that delves into the para‐selective functionalization or dearomatization functionalization of benzene rings, achieved through the reaction of carbenes with allyl sulfoxides. Mechanistic investigations suggest that the transformation likely proceeds via an uncommon carbene‐mediated [4,5]‐rearrangement process.

Selective Functionalization of Benzene Ring via Carbene Initiated [4,5]‐Rearrangement

2025-06-17

Jiarong Shi , Xuerong Wang , Chuang Mei +4 more | Angewandte Chemie International Edition

Copper‐Catalyzed Coupling Reaction of Diazo Reagent with Formamide for the Synthesis of α‐Formyloxy Ketones and α‐Ketoamides

2025-06-16

Rongxiang Chen , Jutuan Xiao , Jing Cao +4 more | Advanced Synthesis & Catalysis

A copper‐catalyzed coupling reaction of diazo reagents with formamides is reported. Under the optimal reaction conditions, this reaction leads to a wide range of α‐formyloxy ketones and α‐ketoamides in moderate … A copper‐catalyzed coupling reaction of diazo reagents with formamides is reported. Under the optimal reaction conditions, this reaction leads to a wide range of α‐formyloxy ketones and α‐ketoamides in moderate to good yields. This strategy enables the installation of two important functional groups, aldehyde and amine group, into the target molecule in the presence of formamide via CN bond cleavage. Mechanism studies indicate that this conversion reaction may undergo a radical process.

Formal Higher‐Order [8 + 3] Cycloaddition of Azaheptafulvenes with Donor‐Acceptor Cyclopropanes

2025-06-16

Junjie Xi , Wang Liu , Guochun Li +6 more | European Journal of Organic Chemistry

Cyclohepta[b]pyridine derivatives have attracted significant attention owing to their unique bioactivities. Herein, we describe an efficient method to access various cyclohepta[b]pyridine derivatives through formal higher‐order [8+3] cycloaddition of azaheptafulvenes with … Cyclohepta[b]pyridine derivatives have attracted significant attention owing to their unique bioactivities. Herein, we describe an efficient method to access various cyclohepta[b]pyridine derivatives through formal higher‐order [8+3] cycloaddition of azaheptafulvenes with donor‐acceptor cyclopropanes catalyzed by Yb(OTf)3. This method exhibited broad substrate accommodation and gave the corresponding products in high yields and selectivity.

Binuclear Copper-Catalyzed Enantioselective C,N-Dipolar (3 + 2) Cycloadditions: Mechanistic Insights and Selectivity Control via DFT Analysis

2025-06-16

Yu Wang , Linxing Zhang , Jia Zhou +1 more | The Journal of Organic Chemistry

2-Aminoallyl cations serve as highly versatile intermediates in organic synthesis. Their cycloaddition with unsaturated compounds provides an efficient strategy for the construction of heterocycles, which are key structural motifs found … 2-Aminoallyl cations serve as highly versatile intermediates in organic synthesis. Their cycloaddition with unsaturated compounds provides an efficient strategy for the construction of heterocycles, which are key structural motifs found in a wide range of natural products, bioactive molecules, and agrochemicals. The mechanism and enantioselectivity of the C,N-dipolar (3 + 2) cycloaddition of 2-aminoallyl cations with indoles have been investigated using density functional theory (DFT). We proposed that binuclear copper-assisted decarboxylation produces the 2-aminoallyl cation from ethynyl methylene cyclic carbamates (EMCCs), which then undergoes an enantioselective (3 + 2) cycloaddition reaction with indoles to yield the final product. Our results indicate that the concerted mechanism is more favorable than the stepwise mechanism. The concerted mechanism involves asynchronous bond formation processes. The enantioselectivity is predominantly governed by the distortion energy. The atomic dipole moment corrected Hirshfeld (ADCH) charge indicates that the regioselectivity is determined by the charge matching principle. The electron-poor carbon (C4: + 0.033) of the indole preferentially reacts with the nitrogen atom (N2: - 1.010) of the dipolar intermediate, leading to the formation of the major product. To validate the binuclear activation hypothesis, we computationally rationalized that chiral benzo[c]cinnoline-dioxazoline-supported binuclear copper catalysts ([L1(Cu)2]2+) exhibit enhanced catalytic efficiency for the C,N-dipolar (3 + 2) cycloaddition reaction.

SYNTHESIS OF PREVIOUSLY UNKNOWN BRIDGED AZABICYCLES BY CATALYTIC CYCLOPADDITION OF ALKYNES TO METHYL 1H-AZEPINE-1-CARBOXYLATE

2025-06-16

Gulnara N. Kadikova | Izvestia Ufimskogo Nauchnogo Tsentra RAN

Cobalt(I)-catalyzed [6π+2π] cycloaddition of terminal alkynes (hexyne-1, 4-pentyn-1-ol, 5-hexynenitrile) to methyl 1H-azepine-1-carboxylate was reported for the first time to afford previously undescribed 9-azabicyclo[4.2.1]nona-2,4,7-trienes in high yields (71–91%). A three-component system … Cobalt(I)-catalyzed [6π+2π] cycloaddition of terminal alkynes (hexyne-1, 4-pentyn-1-ol, 5-hexynenitrile) to methyl 1H-azepine-1-carboxylate was reported for the first time to afford previously undescribed 9-azabicyclo[4.2.1]nona-2,4,7-trienes in high yields (71–91%). A three-component system consisting of a cobalt(II) salt bound to a 1,2-bis(diphenylphosphino)ethane ligand (Co(acac)2(dppe), CoBr2(dppe), CoI2(dppe), CoCl2(dppe)), a Zn reducing agent, and a Lewis acid ZnI2 was used as a catalyst. The highest yield of 9-azabicyclo[4.2.1]nona-2,4,7-trienes is observed when using Co(acac)2(dppe) (88–91%), CoBr2(dppe) (79–89%) and CoI2(dppe) (86–91%) salts as catalysts. In the case of using CoCl2(dppe) the yield of azabicycles decreases (71–77%). According to the analysis of one- and two-dimensional NMR spectra, 9-azabicyclo[4.2.1]nona-2,4,7 trienes are formed as two rotamers in a 1:1 ratio.

Palladium-Catalyzed [3 + 2] Cycloaddition of Vinylethylene Carbonates with In Situ Generated Ketones from Diazo Compounds and DMSO

2025-06-14

Zemin Pan , Liying Fu , Zheng Zhou +3 more | The Journal of Organic Chemistry

The palladium-catalyzed [3 + 2] cycloaddition of vinylethylene carbonates (VECs) with ketones presents significant challenges with only sporadic examples reported. Herein, we have developed an in situ generation strategy enabling … The palladium-catalyzed [3 + 2] cycloaddition of vinylethylene carbonates (VECs) with ketones presents significant challenges with only sporadic examples reported. Herein, we have developed an in situ generation strategy enabling the engagement of polycarbonyl-based ketones in [3 + 2] cycloaddition with VECs. This approach utilizes diazo compounds as latent carbonyl precursors and employs DMSO as both the solvent and oxidant, bypassing issues associated with the isolation of easily hydrated polycarbonyl compounds. By this protocol, various 1,3-dioxolanes bearing two quaternary stereocenters were readily constructed.

Copper-catalyzed synthesis of isoindigoes and isatins from diazo(nitro)acetanilides

2025-06-14

Xuan Ke , Chuangchuang Xu , Jiaxi Xu | Phosphorus, sulfur, and silicon and the related elements

A Synthetic Route to Functionalized Thiopyran Derivatives via Domino Ring-Opening Cyclization (DROC) of Donor–Acceptor Cyclopropanes with Pyridinium Thiolates

2025-06-13

S. P. YADAV , Amit Kumar Sharma , Poulami Mandal +2 more | The Journal of Organic Chemistry

An efficient route to 5,6-dihydro-4H-thiopyran derivatives is developed via domino ring-opening cyclization (DROC) of activated donor-acceptor (DA)-cyclopropanes with pyridinium thiolates in the presence of Yb(OTf)3 as the Lewis acid and … An efficient route to 5,6-dihydro-4H-thiopyran derivatives is developed via domino ring-opening cyclization (DROC) of activated donor-acceptor (DA)-cyclopropanes with pyridinium thiolates in the presence of Yb(OTf)3 as the Lewis acid and K2CO3 as the base under mild conditions in moderate to excellent yields. Enantiospecific SN2-type DROC of nonracemic DA-cyclopropane (ee 97%) with pyridinium thiolate afforded the corresponding nonracemic thiopyran product with high yield and excellent enantiospecificity (>97%). This approach offers a straightforward and practical route to thiopyran frameworks of synthetic and biological significance.

Oxygen transposition of formamide to α-aminoketone moiety in a carbene-initiated domino reaction

2025-06-13

Yan Luo , Guanglong Huang , K. Ding +2 more | Nature Chemistry

Relay Rh(II)/Pd(0) Dual-Catalyzed Three-Component Allylation of α-Diazo Carbonyl Compounds via Ketene Intermediates: Construction of All-Carbon Quaternary Centers

2025-06-11

Yuhua Song , Xiaoyan Huang , Baoxiu Mi +4 more | Organic Letters

A relay Rh(II)/Pd(0) dual-catalyzed three-component allylic alkylation of alcohols, α-diazo 1,3-diketones, and allyl reagents is successfully developed, which provides a highly chemoselective method for the one-pot synthesis of acyclic α-quaternary … A relay Rh(II)/Pd(0) dual-catalyzed three-component allylic alkylation of alcohols, α-diazo 1,3-diketones, and allyl reagents is successfully developed, which provides a highly chemoselective method for the one-pot synthesis of acyclic α-quaternary allylated β-keto-esters. Remarkably, this transformation includes difunctionalizations of ketene intermediates instead of metal-carbene intermediates. Our protocol is characterized by mild conditions, simple raw materials, and good to excellent yields.

Cu-Catalyzed Electrochemical Atom Transfer Radical Addition with Halomalonic Esters: A Route to Cyclopropane Derivatives

2025-06-05

Chuyi Su , Masnun Naher , Craig M. Williams +1 more | The Journal of Organic Chemistry

Atom transfer radical addition (ATRA) remains an important and popular synthetic method for C-C bond formation by using readily accessible alkene precursors and organic halides. We report that copper-catalyzed electrochemical … Atom transfer radical addition (ATRA) remains an important and popular synthetic method for C-C bond formation by using readily accessible alkene precursors and organic halides. We report that copper-catalyzed electrochemical ATRA (eATRA) of diethyl halomalonates (XCH(COOEt)2, X = Br, Cl) to a series of aromatic alkenes yields halide malonate ester intermediates that subsequently undergo facile ring closure to give cyclopropanes. The in situ spectroscopic identification of a diethyl malonatocopper(II) complex, [CuIIL(CH(COOEt)2)]+, serves as a key catalytic species, effectively moderating free radical concentrations during the electrochemical process to enhance product formation. Mechanistic insights into cyclopropanation were elucidated through cyclic voltammetry and UV-vis spectroelectrochemical analysis. This study presents a new mild electrochemical synthetic strategy for constructing functionalized cyclopropane derivatives.

Copper‐Catalyzed Cyclopropanation Reaction of Indoles through Diyne Cyclization

2025-06-04

Fu‐Shuai Li , En‐He Huang , Zhen-Zhen Ge +5 more | Chinese Journal of Chemistry

Comprehensive Summary Transition metal‐catalyzed cyclopropanation reactions of indoles are generally limited to diazo compounds. Herein, an efficient copper‐catalyzed cyclopropanation reaction of indoles with N ‐propargyl ynamides is demonstrated, allowing for … Comprehensive Summary Transition metal‐catalyzed cyclopropanation reactions of indoles are generally limited to diazo compounds. Herein, an efficient copper‐catalyzed cyclopropanation reaction of indoles with N ‐propargyl ynamides is demonstrated, allowing for practical and atom‐economic construction of valuable cyclopropa[ b ]indolines in generally moderate to excellent yields under mild reaction conditions. Thus, this reaction constitutes a new way for cyclopropanation of indoles involving vinyl cations generated from diyne cyclization as key intermediates. Moreover, such an asymmetric cyclopropanation of indoles via chiral copper catalysis has also been realized. In addition, the formal C(sp 2 )–H functionalization of indoles is achieved by a one‐pot copper‐catalyzed diyne cyclization followed by proton acid‐mediated ring‐opening of cyclopropanes.

ZnBr2 catalyzed sequential A3-coupling and intramolecular cyclization: One-pot synthesis of 3-aminofurans

2025-06-01

Battini Geetha Rani , Sreedhar Gundekari , K. Ramesh +2 more | Tetrahedron Letters

Two-Step Benzo[e]indole Core Assemblage from Three 1H-1,2,3-Triazole Molecules via “Transannulation/C–H Insertion/SEAr–Cyclization” Sequence

2025-05-31

Ivan V. Simdianov , Pavel А. Sakharov , Alexander F. Khlebnikov +3 more | The Journal of Organic Chemistry

A two-step synthesis of fluorescent 2,3-dihydrobenzo[e]indole derivatives using only 1H-1,2,3-triazoles as starting materials was developed. At the first step of the synthesis, the 1-alkyl-1,2,3-triazole reacts with two 1-sulfonyl-1,2,3-triazole molecules via … A two-step synthesis of fluorescent 2,3-dihydrobenzo[e]indole derivatives using only 1H-1,2,3-triazoles as starting materials was developed. At the first step of the synthesis, the 1-alkyl-1,2,3-triazole reacts with two 1-sulfonyl-1,2,3-triazole molecules via the domino transannulation/sulfonamidovinylation sequence under rhodium catalysis. The reaction involving two different 1-sulfonyltriazoles is accomplished in one pot. The further SEAr cyclization of the formed 4-aryl-5-(sulfonamidovinyl)pyrroles using Eaton's reagent provides 2,3-dihydrobenzo[e]indoles having a sulfonylimino-, hydroxy-, and primary amino groups at the C1, C2, and C5 positions, respectively.

Water‐Catalytic Deconstructive and Proton Transfer Cyclopropanation of Sulfoxonium Ylide with Olefin

2025-05-30

Xianglin Yu , Liuting Huang , Haiyue Yang +2 more | Advanced Science

Abstract Cyclopropane rings, with their distinct structure and reactivity, have long been a focus in organic chemistry and are significant pharmacophores in medicinal chemistry. Conventional direct cyclopropanation methods for olefins … Abstract Cyclopropane rings, with their distinct structure and reactivity, have long been a focus in organic chemistry and are significant pharmacophores in medicinal chemistry. Conventional direct cyclopropanation methods for olefins do not modify the functional groups on the α ‐ or β ‐carbon of olefins. Herein, a novel deconstructive cyclopropanation reaction is designed for olefins using a close–open–close ring strategy. This enables the migration of functional groups to the α ‐ or β ‐carbon of olefins, leading to the formation of regioselective cyclopropane compounds, which is a previously unreported approach. By exploiting the zwitterionic property of sulfoxonium ylides and combining them with Density Functional Theory (DFT) computations, the reaction is proposed to proceed via a [2 + 2] cycloaddition to form a strained cyclobutene intermediate, followed by cyclobutane ring‐opening and nucleophilic substitution through a water‐involved proton‐shuttle process for ring closure. Hydrogen‐bonding interactions play a significant role in controlling the regioselectivity.

Asymmetric Remote Leaving Group-Promoted Propargylic Substitution

2025-05-29

Yuanxiang Yang , Yifan Wang , Guoqiang Lin +1 more | ACS Catalysis

TiCl4-Mediated Diastereoselective Tandem Reactions of Functionalized Keto Esters and Dihydrofurans: Synthesis of Substituted Tricyclic Hexahydro-2H-benzocycloheptafurans

2025-05-29

Arun K. Ghosh , Tristan John McDonald , Nilanjana Chakraborty | The Journal of Organic Chemistry

We report highly diastereoselective TiCl4-mediated tandem reactions that provide functionalized tricyclic benzocycloheptafurans in an efficient manner. The reaction of a range of substituted α-keto esters with dihydrofuran or phenyl dihydrofuran … We report highly diastereoselective TiCl4-mediated tandem reactions that provide functionalized tricyclic benzocycloheptafurans in an efficient manner. The reaction of a range of substituted α-keto esters with dihydrofuran or phenyl dihydrofuran in CH2Cl2 set up a tandem reaction sequence, providing fused ring heterocycles. The precursor-substituted keto esters were synthesized efficiently by using a two-step sequence. The reaction accessed relatively unexplored hexahydro-2H-benzocycloheptafuran ring systems with three contiguous chiral centers, providing excellent diastereoselectivity and good to excellent yields. A metal triflate catalyzed acyloxy oxocarbenium-mediated ring opening of the tandem reaction products also provided convenient access to substituted benzo[7]annulene cores.

Tunable Endo/Exo Selectivity in Direct Catalytic Asymmetric 1,3‐Dipolar Cycloadditions with Polyfunctional Lewis Acid / Azolium‐Aryloxide Catalysts

2025-05-28

Adrian Bürstner , Patrick Becker , Alexander Allgaier +7 more | Angewandte Chemie International Edition

Catalytic asymmetric 1,3‐dipolar cycloadditions (1,3‐DCA) using iminoesters as ylide precursors offer a powerful approach to accessing stereochemically complex, biologically relevant pyrrolidines. While previous studies have already achieved impressive stereoselectivities, catalytic … Catalytic asymmetric 1,3‐dipolar cycloadditions (1,3‐DCA) using iminoesters as ylide precursors offer a powerful approach to accessing stereochemically complex, biologically relevant pyrrolidines. While previous studies have already achieved impressive stereoselectivities, catalytic productivity remains a challenge, with turnover numbers (TON) typically below 20. In this article, we introduce a novel concept for catalytic 1,3‐DCA that enables remarkable productivity for both endo (TON up to 4000) and the more challenging exo products (TON up to 1500). This approach making use of modular polyfunctional Lewis acid/azolium‐aryloxide catalysts allows for precise control over endo‐ and exo‐diastereoselectivity. The switch from endo‐ to exo‐selectivity is accomplished by modifying the metal center, the azolium moiety and steric factors. As detailed DFT studies reveal, both the endo‐ and exo‐selective catalyst systems exhibit an almost perfect spatial alignment of their key functional sites, allowing for a unique interplay of Brønsted acids and bases, Lewis acids, and hydrogen bonding. The computational studies further demonstrate that these polyfunctional catalysts dramatically lower the energetic barriers of the concerted or stepwise cycloaddition key steps. However, they also precisely orchestrate and accelerate all accompanying transformations—reminiscent of enzymatic machineries.

Tunable Endo/Exo Selectivity in Direct Catalytic Asymmetric 1,3‐Dipolar Cycloadditions with Polyfunctional Lewis Acid / Azolium‐Aryloxide Catalysts

2025-05-28

Adrian Bürstner , Patrick Becker , Alexander Allgaier +7 more | Angewandte Chemie

Construction of Chiral Tricyclic Structures Using Whole‐Cell Biocatalysts: A Strategy via the Cyclopropanation of Unsaturated π‐Systems

2025-05-28

Fengxi Li , Qikai Sun , Ziyang Yu +6 more | Chinese Journal of Chemistry

Comprehensive Summary Chiral tricyclic compounds represent a significant class of biologically active substances with wide‐ranging applications in materials science, medicinal chemistry, as well as the food and fragrance industries. Here, … Comprehensive Summary Chiral tricyclic compounds represent a significant class of biologically active substances with wide‐ranging applications in materials science, medicinal chemistry, as well as the food and fragrance industries. Here, we combine CAST (combinatorial active site saturation test) and bacterial surface display technology to develop a laboratory‐evolved whole‐cell catalyst, designated SD‐VHb Tric (surface display of vitreoscilla hemoglobin). This novel carbene‐transferase is based on the engineered VHb and employs a strategy for the cyclopropanation of unsaturated π‐systems to synthesize various chiral tricyclic structures. SD‐VHb Tric exhibits unparalleled stereocontrol (up to 99.9% de and 99% ee ) and good reactivity, enabling the synthesis of chiral tricyclic structures with diverse aromatic or heterocyclic ring scaffolds from simple starting materials. Additionally, computational studies were conducted to elucidate the crucial role of intermolecular hydrophobic interactions in regulating the reaction, while also demonstrating the significant impact of adaptive changes in the active pocket size on the orientation of the ligand.

Flash Communication: N-Heterocyclic Carbene Nickel-Mediated C–C Activation of Substituted Vinylcyclobutanes

2025-05-28

Cherish Nie , Marina Pérez‐Jiménez , Junho Kim +1 more | Organometallics

Chiral cyclopropanes with light in confined space

2025-05-28

Magdalena Walewska-Królikiewicz , Dorota Gryko | Nature Catalysis