Chemistry › Organic Chemistry

Asymmetric Synthesis and Catalysis

Works Count: 68875

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This cluster of papers covers recent advances in asymmetric catalysis, including organocatalysis, enantioselective reactions, chiral catalysts, asymmetric synthesis, C-C bond formation, spirooxindoles, hydrogen bonding, transition metal catalysis, quaternary stereocenters, and cascade reactions.

Keywords

Organocatalysis; Enantioselective Reactions; Chiral Catalysts; Asymmetric Synthesis; C-C Bond Formation; Spirooxindoles; Hydrogen Bonding; Transition Metal Catalysis; Quaternary Stereocenters; Cascade Reactions

Catalytic C–C Bond-Forming Multi-Component Cascade or Domino Reactions: Pushing the Boundaries of Complexity in Asymmetric Organocatalysis

2013-12-04

Chandra M. R. Volla , Iuliana Atodiresei , Magnus Rueping

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCatalytic C–C Bond-Forming Multi-Component Cascade or Domino Reactions: Pushing the Boundaries of Complexity in Asymmetric OrganocatalysisChandra M. R. Volla, Iuliana Atodiresei, and Magnus Rueping*View Author Information Institute … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCatalytic C–C Bond-Forming Multi-Component Cascade or Domino Reactions: Pushing the Boundaries of Complexity in Asymmetric OrganocatalysisChandra M. R. Volla, Iuliana Atodiresei, and Magnus Rueping*View Author Information Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany*E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 4, 2390–2431Publication Date (Web):December 4, 2013Publication History Received22 April 2013Published online4 December 2013Published inissue 26 February 2014https://pubs.acs.org/doi/10.1021/cr400215uhttps://doi.org/10.1021/cr400215ureview-articleACS PublicationsCopyright © 2013 American Chemical SocietyRequest reuse permissionsArticle Views18477Altmetric-Citations951LEARN 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,Aldehydes,Catalysts,Chemical reactions,Stereoselectivity Get e-Alerts

Proline-Catalyzed Direct Asymmetric Aldol Reactions

2000-02-26

Benjamin List , Richard A. Lerner , Carlos F. Barbas

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTProline-Catalyzed Direct Asymmetric Aldol ReactionsBenjamin List, Richard A. Lerner, and Carlos F. BarbasView Author Information The Skaggs Institute for Chemical Biology and the Department of Molecular Biology … ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTProline-Catalyzed Direct Asymmetric Aldol ReactionsBenjamin List, Richard A. Lerner, and Carlos F. BarbasView Author Information The Skaggs Institute for Chemical Biology and the Department of Molecular Biology The Scripps Research Institute 10550 North Torrey Pines Road, La Jolla, California 92037 Cite this: J. Am. Chem. Soc. 2000, 122, 10, 2395–2396Publication Date (Web):February 26, 2000Publication History Received7 December 1999Published online26 February 2000Published inissue 1 March 2000https://pubs.acs.org/doi/10.1021/ja994280yhttps://doi.org/10.1021/ja994280yrapid-communicationACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views92128Altmetric-Citations2513LEARN 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:Aldol reactions,Catalysts,Ketones,Peptides and proteins,Stereoselectivity Get e-Alerts

Catalytic Asymmetric Synthesis of Oxindoles Bearing a Tetrasubstituted Stereocenter at the C‐3 Position

2010-05-28

Feng Zhou , Yun‐Lin Liu , Jian Zhou

Abstract The 3,3′‐disubstituted oxindole structural motif is a prominent feature in many alkaloid natural products, which include all kinds of tetrasubstituted carbon stereocenters, spirocyclic or not, all‐carbon or heteroatom‐containing. The … Abstract The 3,3′‐disubstituted oxindole structural motif is a prominent feature in many alkaloid natural products, which include all kinds of tetrasubstituted carbon stereocenters, spirocyclic or not, all‐carbon or heteroatom‐containing. The catalytic asymmetric synthesis of the tetrasubstituted carbon stereocenter at the C‐3 position of the oxindole framework integrates new synthetic methods and chiral catalysts, reflects the latest achievements in asymmetric catalysis, and facilitates the synthesis of sufficient quantities of related compounds as potential medicinal agents and biological probes. This review summarizes the recent progress in this area, and applications in the total synthesis of related bioactive compounds.

Asymmetric Enamine Catalysis

2007-12-01

Santanu Mukherjee , Jung Woon Yang , S.D. Hoffmann +1 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric Enamine CatalysisSantanu Mukherjee, Jung Woon Yang, Sebastian Hoffmann, and Benjamin ListView Author Information Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany Cite this: Chem. Rev. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric Enamine CatalysisSantanu Mukherjee, Jung Woon Yang, Sebastian Hoffmann, and Benjamin ListView Author Information Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany Cite this: Chem. Rev. 2007, 107, 12, 5471–5569Publication Date (Web):December 12, 2007Publication History Received28 August 2007Published online12 December 2007Published inissue 1 December 2007https://pubs.acs.org/doi/10.1021/cr0684016https://doi.org/10.1021/cr0684016research-articleACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views56266Altmetric-Citations2550LEARN 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:Aldehydes,Aldol reactions,Catalysts,Ketones,Stereoselectivity Get e-Alerts

Stronger Brønsted Acids

2007-11-06

Takahiko Akiyama

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStronger Brønsted AcidsTakahiko AkiyamaView Author Information Department of Chemistry, Faculty of Science, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo 171-8588, Japan Cite this: Chem. Rev. 2007, 107, 12, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStronger Brønsted AcidsTakahiko AkiyamaView Author Information Department of Chemistry, Faculty of Science, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo 171-8588, Japan Cite this: Chem. Rev. 2007, 107, 12, 5744–5758Publication Date (Web):November 6, 2007Publication History Received9 May 2007Published online6 November 2007Published inissue 1 December 2007https://pubs.acs.org/doi/10.1021/cr068374jhttps://doi.org/10.1021/cr068374jresearch-articleACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views24675Altmetric-Citations2065LEARN 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:Brønsted acid,Catalysts,Reaction products,Stereoselectivity,Transfer reactions Get e-Alerts

1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis

1996-01-01

David J. Ager , Indra Prakash , David R. Schaad

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric SynthesisDavid J. Ager, Indra Prakash, and David R. SchaadView Author Information NSC Technologies, and NutraSweet Kelco … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric SynthesisDavid J. Ager, Indra Prakash, and David R. SchaadView Author Information NSC Technologies, and NutraSweet Kelco Units of Monsanto, 601 East Kensington Road, Mount Prospect, Illinois 60056 Cite this: Chem. Rev. 1996, 96, 2, 835–876Publication Date (Web):March 28, 1996Publication History Received5 September 1995Revised8 November 1995Published online28 March 1996Published inissue 1 January 1996https://pubs.acs.org/doi/10.1021/cr9500038https://doi.org/10.1021/cr9500038research-articleACS PublicationsRequest reuse permissionsArticle Views15721Altmetric-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 InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Alcohols,Anions,Enolates,Reaction products,Selectivity Get e-Alerts

Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts

2003-09-30

Tomotaka Okino , Yasutaka Hoashi , Yoshiji Takemoto

Michael reaction of malonates to nitroolefins with chiral bifunctional organocatalysts, bearing both a thiourea and tertiary amino group, afforded Michael adducts with high yields and enantioselectivities (up to 95%, up … Michael reaction of malonates to nitroolefins with chiral bifunctional organocatalysts, bearing both a thiourea and tertiary amino group, afforded Michael adducts with high yields and enantioselectivities (up to 95%, up to 93% ee).

Recent Advances in Asymmetric Organocatalytic 1,4‐Conjugate Additions

2007-03-01

Svetlana B. Tsogoeva

Abstract Recent progress in the field of asymmetric organocatalytic 1,4‐conjugate addition reactions, regarded as belonging among the more synthetically important carbon–carbon bond‐forming reactions, is described. The focus is on some … Abstract Recent progress in the field of asymmetric organocatalytic 1,4‐conjugate addition reactions, regarded as belonging among the more synthetically important carbon–carbon bond‐forming reactions, is described. The focus is on some recent advances in the following selected reactions: additions of various nucleophiles to α,β‐unsaturated cyclic and acyclic enals, enones, vinyl sulfones and nitro olefins, addition of malonates and/or ketones to acyclic enones, or of aldehydes and ketones to vinyl ketones and nitro olefins, together with some multicomponent domino reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Enantioselective Mannich‐Type Reaction Catalyzed by a Chiral Brønsted Acid

2004-03-09

Takahiko Akiyama , Junji Itoh , Koji Yokota +1 more

No metal required: The Mannich-type reaction of ketene silyl acetals 2 with aldimines 1 proceeded highly enantioselectively to afford the syn isomer of β-aminoesters 3 with up to 96 % … No metal required: The Mannich-type reaction of ketene silyl acetals 2 with aldimines 1 proceeded highly enantioselectively to afford the syn isomer of β-aminoesters 3 with up to 96 % ee under the influence of a chiral Brønsted acid 4 derived from (R)-BINOL. The enantioselective Mannich-type reaction of an enolate or an enolate anion equivalent with aldimines constitutes a useful method for the preparation of chiral β-amino carbonyl compounds, which are the precursors of biologically important compounds such as β-lactams and β-amino acids. The development of chiral catalysts for the asymmetric Mannich-type reaction has attracted the attention of synthetic organic chemists.1 Although stoichiometric amounts of chiral acid were employed initially,2 a number of enantioselective catalysts such as chiral Lewis acid catalysts3 and chiral base catalysts4 have been developed lately. In addition to metal-based chiral catalysts,5 the use of small organic molecules as catalysts to promote asymmetric reactions has emerged as a new frontier in reaction methodology.6 Accordingly, L-proline derivatives7 and peptide derivatives8 have been developed as catalysts for the Mannich-type reactions. We previously reported that Mannich-type reactions9 and the aza-Diels–Alder reaction10 proceed smoothly in the presence of a catalytic amount of a strong Brønsted acid. We thus postulated that the use of a chiral Brønsted acid, in which the proton is surrounded by bulky substituents, may lead to effective asymmetric induction. We report herein an enantioselective Mannich-type reaction of silyl enolates with aldimines catalyzed by a chiral metal-free Brønsted acid.11, 12 First, treatment of aldimine 1 a (Scheme 1, R1=Ph) and ketene silyl acetal 2 (3.0 equiv) with 0.3 equivalents of the chiral phosphate 4 a13, 14, 15 (which is readily prepared from (R)-BINOL; Scheme 2) in toluene at −78 °C led to a smooth Mannich-type reaction to give 3 a (R1=Ph). However, no enantioselectivity was observed (Table 1, entry 1), as determined by HPLC analysis with a chiral stationary phase column.16 Next, we synthesized chiral phosphates 4 b–e by Suzuki coupling of bis(boronic acid) 517 followed by demethylation and subsequent phosphorylation, as shown in Scheme 2. Introduction of aromatic groups at the 3,3′-positions exerted a beneficial effect on the enantioselectivity. Use of 4 b as a chiral Brønsted acid in toluene increased the enantiofacial selectivity to 27 % ee (Table 1, entry 2). The introduction of 4-nitrophenyl groups (i.e. 4 e) had a dual effect: 1) improvement of enantioselectivity to 87 % ee, 2) acceleration of reaction rate, thereby allowing the reaction to go to completion in 4 h (Table 1, entry 5). The absolute stereochemistry of 3 a was determined by chiral HPLC analysis by comparison of the retention time with that found in the literature.3c Mannich-type reaction of aldimines 1 and ketene silyl acetals 2 to form β-aminoesters 3. Formation of chiral phosphates 4, readily available from (R)-BINOL. Entry Ar t [h] Yield [%] ee [%] 1 H 22 57 0 2 Ph 20 100 27 3 2,4,6-Me3C6H2 27 100 60 4 4-MeOC6H4 46 99 52 5 4-NO2C6H4 4 96 87 By further optimization of the reaction conditions, we found that the use of aromatic solvents led to high enantioselectivities, whereas protic solvents gave racemates.18 Furthermore, a lower loading (10 mol %) of the Brønsted acid was sufficient to retain the high enantioselectivity. The results of the Mannich-type reaction of 2 with several aldimines catalyzed by chiral Brønsted acid 4 e are shown in Table 2. Aldimines derived from aromatic aldehydes afforded adducts with good to high enantioselectivities. The chemical yields were excellent in all cases.19, 20 Entry R1 Product Yield [%] ee [%] 1 Ph 3 a 98 89 2 p-MeC6H4 3 b 100 89 3 p-FC6H4 3 c 100 85 4 p-ClC6H4 3 d 100 80 Next, other ketene silyl acetals were examined (Table 3). Monosubstituted ketene silyl acetals led to high syn selectivity as well as excellent enantioselectivity. The ketene silyl acetal derived from ethyl propionate furnished the corresponding ester in 96 % ee (Table 3, entry 1). Substituted aromatic, heteroaromatic, and α,β-unsaturated aldimines also gave the corresponding adducts with high enantioselectivities (Table 3, entries 2–7). The reactions of ketene silyl acetals derived from ethyl 3-phenylpropionate (Table 3, entries 8–10) and methyl 2-triphenylsilyloxyacetate (Table 3, entry 11) also exhibited excellent syn selectivities21 and high enantioselectivities. Entry R1 R2 R3 Yield [%] syn/anti ee [%][b] 1 Ph Me[c] Et 100 87:13 96 2 p-MeOC6H4 Me[c] Et 100 92:8 88 3 p-FC6H4 Me[c] Et 100 91:9 84 4 p-ClC6H4 Me[c] Et 100 86:14 83 5 p-MeC6H4 Me[c] Et 100 94:6 81 6 2-Thienyl Me[c] Et 81 94:6 88 7 PhCHCH Me[c] Et 91 95:5 90 8 Ph PhCH2[d] Et 100 93:7 91 9 p-MeOC6H4 PhCH2[d] Et 92 93:7 87 10 PhCHCH PhCH2[d] Et 65 95:5 90 11 Ph Ph3SiO[e] Me 79 100:0 91 Because the use of N-benzylideneaniline in place of 1 a (R1=Ph) in the reaction with 2 lowered the enantioselectivity to 39 % ee, we concluded that the presence of the hydroxy group in the ortho position of the aldimine is essential for the present enantioselective Mannich-type reaction. This reaction can be considered to proceed via an iminium salt, generated from the aldimine and the Brønsted acid. Although the precise mechanism has not been elucidated, it is supposed that 3,3′-diaryl groups, which are not coplanar with the naphthyl groups (see 8-1 ), would effectively shield the phosphate moiety, leading to efficient asymmetric induction.22 This is the first example of an enantioselective Mannich-type reaction in which the carbon–nitrogen double bond is activated by a strong, metal-free chiral Brønsted acid, even though chiral Brønsted acids were previously implicated in enantioselective Mannich-type reactions.7, 8 In summary, we have developed a chiral Brønsted acid catalyzed enantioselective Mannich-type reaction of aldimines with silyl enolates, and β-aminoesters were obtained with high to excellent enantioselectivities under metal-free conditions. This method adds a new entry to the catalogue organo-catalyzed asymmetric reactions. This method can potentially be extended to a variety of enantioselective nucleophilic addition reactions to carbon–nitrogen double bonds. Further investigations to clarify the reaction mechanism and its application to other enantioselective reactions are in progress. General procedure (Table 3, Entry 1): A solution of 6 (R2=Me, R3=Et) (50 μL, 0.246 mmol) was added dropwise over 3 min to a solution of 1 (R1=Ph) (32.0 mg, 0.162 mmol) and 4 e (9.5 mg, 0.0161 mmol) in toluene (1 mL) at −78 °C. The reaction was stirred at this temperature for 17 h. The mixture was quenched by the addition of saturated solutions of NaHCO3 and KF at −78 °C. After filtration over celite, the filtrate was extracted with ethyl acetate. The combined organic layers were washed successively washed with HCl (1 n) and brine, dried over anhydrous Na2SO4, and concentrated to dryness. The remaining solid was purified by TLC (SiO2, hexane/EtOAc 3:1) to give 7 (45.6 mg, 0.155 mmol) in 100 % yield. The enantiomeric excess was determined on a Daicel Chiralpak AS-H column.

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In the Golden Age of Organocatalysis

2004-09-29

Peter I. Dalko , Lionel Moisan

The term "organocatalysis" describes the acceleration of chemical reactions through the addition of a substoichiometric quantity of an organic compound. The interest in this field has increased spectacularly in the … The term "organocatalysis" describes the acceleration of chemical reactions through the addition of a substoichiometric quantity of an organic compound. The interest in this field has increased spectacularly in the last few years as result of both the novelty of the concept and, more importantly, the fact that the efficiency and selectivity of many organocatalytic reactions meet the standards of established organic reactions. Organocatalytic reactions are becoming powerful tools in the construction of complex molecular skeletons. The diverse examples show that in recent years organocatalysis has developed within organic chemistry into its own subdiscipline, whose "Golden Age" has already dawned.

Advances in the Chemistry of Tetrahydroquinolines

2011-08-10

Vellaisamy Sridharan , Padmakar A. Suryavanshi , J. Carlos Menéndez

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTAdvances in the Chemistry of TetrahydroquinolinesVellaisamy Sridharan, Padmakar A. Suryavanshi, and J. Carlos Menéndez*View Author Information Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense, … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTAdvances in the Chemistry of TetrahydroquinolinesVellaisamy Sridharan, Padmakar A. Suryavanshi, and J. Carlos Menéndez*View Author Information Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense, 28040 Madrid, Spain.E-mail: [email protected]Cite this: Chem. Rev. 2011, 111, 11, 7157–7259Publication Date (Web):August 10, 2011Publication History Received13 September 2010Published online10 August 2011Published inissue 9 November 2011https://pubs.acs.org/doi/10.1021/cr100307mhttps://doi.org/10.1021/cr100307mreview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views21736Altmetric-Citations889LEARN 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,Hydrogenation,Quinolines,Reaction products Get e-Alerts

Metal‐Catalyzed Enantioselective Allylation in Asymmetric Synthesis

2007-10-29

Zhan Lu , Shengming Ma

Metal-catalyzed enantioselective allylation, which involves the substitution of allylic metal intermediates with a diverse range of different nucleophiles or S(N)2'-type allylic substitution, leads to the formation of C-H, -C, -O, … Metal-catalyzed enantioselective allylation, which involves the substitution of allylic metal intermediates with a diverse range of different nucleophiles or S(N)2'-type allylic substitution, leads to the formation of C-H, -C, -O, -N, -S, and other bonds with very high levels of asymmetric induction. The reaction may tolerate a broad range of functional groups and has been applied successfully to the synthesis of many natural products and new chiral compounds.

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Five-membered heteroaromatic rings as intermediates in organic synthesis

1986-10-01

Bruce H. Lipshutz

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFive-membered heteroaromatic rings as intermediates in organic synthesisBruce H. LipshutzCite this: Chem. Rev. 1986, 86, 5, 795–819Publication Date (Print):October 1, 1986Publication History Published online1 May 2002Published inissue … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFive-membered heteroaromatic rings as intermediates in organic synthesisBruce H. LipshutzCite this: Chem. Rev. 1986, 86, 5, 795–819Publication Date (Print):October 1, 1986Publication History Published online1 May 2002Published inissue 1 October 1986https://pubs.acs.org/doi/10.1021/cr00075a005https://doi.org/10.1021/cr00075a005research-articleACS PublicationsRequest reuse permissionsArticle Views5294Altmetric-Citations1074LEARN 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

Amino Acid Catalyzed Direct Asymmetric Aldol Reactions: A Bioorganic Approach to Catalytic Asymmetric Carbon−Carbon Bond-Forming Reactions

2001-05-09

Kandasamy Sakthivel , Wolfgang Notz , Tommy Bui +1 more

Direct asymmetric catalytic aldol reactions have been successfully performed using aldehydes and unmodified ketones together with commercially available chiral cyclic secondary amines as catalysts. Structure-based catalyst screening identified l-proline and … Direct asymmetric catalytic aldol reactions have been successfully performed using aldehydes and unmodified ketones together with commercially available chiral cyclic secondary amines as catalysts. Structure-based catalyst screening identified l-proline and 5,5-dimethyl thiazolidinium-4-carboxylate (DMTC) as the most powerful amino acid catalysts for the reaction of both acyclic and cyclic ketones as aldol donors with aromatic and aliphatic aldehydes to afford the corresponding aldol products with high regio-, diastereo-, and enantioselectivities. Reactions employing hydroxyacetone as an aldol donor provide anti-1,2-diols as the major product with ee values up to >99%. The reactions are assumed to proceed via a metal-free Zimmerman−Traxler-type transition state and involve an enamine intermediate. The observed stereochemistry of the products is in accordance with the proposed transition state. Further supporting evidence is provided by the lack of nonlinear effects. The reactions tolerate a small amount of water (<4 vol %), do not require inert reaction conditions and preformed enolate equivalents, and can be conveniently performed at room temperature in various solvents. In addition, reaction conditions that facilitate catalyst recovery as well as immobilization are described. Finally, mechanistically related addition reactions such as ketone additions to imines (Mannich-type reactions) and to nitro-olefins and α,β-unsaturated diesters (Michael-type reactions) have also been developed.

Catalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and Ketones

2003-07-03

Scott E. Denmark , Jiping Fu

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and KetonesScott E. Denmark and Jiping FuView Author Information Roger Adams Laboratory, Department of Chemistry, University of Illinois, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and KetonesScott E. Denmark and Jiping FuView Author Information Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801 Cite this: Chem. Rev. 2003, 103, 8, 2763–2794Publication Date (Web):July 3, 2003Publication History Received29 January 2003Published online3 July 2003Published inissue 1 August 2003https://pubs.acs.org/doi/10.1021/cr020050hhttps://doi.org/10.1021/cr020050hresearch-articleACS PublicationsCopyright © 2003 American Chemical SocietyRequest reuse permissionsArticle Views13081Altmetric-Citations1110LEARN 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:Aldehydes,Allylation,Catalysts,Chemical structure,Stereoselectivity Get e-Alerts

Asymmetric synthesis of bicyclic intermediates of natural product chemistry

1974-06-01

Zoltan G. Hajos , David R. Parrish

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric synthesis of bicyclic intermediates of natural product chemistryZoltan G. Hajos and David R. ParrishCite this: J. Org. Chem. 1974, 39, 12, 1615–1621Publication Date (Print):June 1, 1974Publication … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric synthesis of bicyclic intermediates of natural product chemistryZoltan G. Hajos and David R. ParrishCite this: J. Org. Chem. 1974, 39, 12, 1615–1621Publication Date (Print):June 1, 1974Publication History Published online1 May 2002Published inissue 1 June 1974https://pubs.acs.org/doi/10.1021/jo00925a003https://doi.org/10.1021/jo00925a003research-articleACS PublicationsRequest reuse permissionsArticle Views15801Altmetric-Citations1120LEARN 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

Organocatalytic cascade reactions as a new tool in total synthesis

2010-02-19

Christoph Grondal , Matthieu Jeanty , Dieter Enders

Proline-catalyzed asymmetric reactions

2002-07-01

Benjamin List

Asymmetric Transition-Metal-Catalyzed Allylic Alkylations: Applications in Total Synthesis

2003-06-21

Barry M. Trost , Matthew L. Crawley

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric Transition-Metal-Catalyzed Allylic Alkylations: Applications in Total SynthesisBarry M. Trost and Matthew L. CrawleyView Author Information Department of Chemistry, Stanford University, Stanford, California 94305-5080 Cite this: Chem. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric Transition-Metal-Catalyzed Allylic Alkylations: Applications in Total SynthesisBarry M. Trost and Matthew L. CrawleyView Author Information Department of Chemistry, Stanford University, Stanford, California 94305-5080 Cite this: Chem. Rev. 2003, 103, 8, 2921–2944Publication Date (Web):June 21, 2003Publication History Received21 January 2003Published online21 June 2003Published inissue 1 August 2003https://pubs.acs.org/doi/10.1021/cr020027whttps://doi.org/10.1021/cr020027wresearch-articleACS PublicationsCopyright © 2003 American Chemical SocietyRequest reuse permissionsArticle Views34612Altmetric-Citations2528LEARN 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:Alcohols,Ligands,Organic synthesis,Post-translational modification,Substitution reactions Get e-Alerts

Organocatalysis—after the gold rush

2009-01-01

Søren Bertelsen , Karl Anker Jørgensen

The use of secondary amines as asymmetric catalysts in transformations of carbonyl compounds has seen tremendous development in recent years. Going from sporadic reports of selected reactions, aminocatalysis can now … The use of secondary amines as asymmetric catalysts in transformations of carbonyl compounds has seen tremendous development in recent years. Going from sporadic reports of selected reactions, aminocatalysis can now be considered as one of the methods of choice for many asymmetric functionalizations of carbonyl compounds--primarily of aldehydes and ketones. These functionalizations have been published at a breathtaking pace over the last few years--during the "golden age" and "gold rush" of organocatalysis. This tutorial review will firstly sketch the basic developments in organocatalysis, focussing especially on the use of secondary amines as catalysts for the functionalization of aldehydes and alpha,beta-unsaturated aldehydes, with emphasis on the mechanisms of the transformations and, secondly, outline recent trends within central areas of this research topic. Lastly, we will present our guesses as to where new developments might take organocatalysis in the years to come.

Modern Variants of the Mannich Reaction

1998-05-04

Michael Arend , Bernhard Westermann , Nikolaus Risch

Important building blocks for the synthesis of drugs or natural products are found in Mannich bases and their derivatives. Modern variants of the Mannich reaction that expand the potential of … Important building blocks for the synthesis of drugs or natural products are found in Mannich bases and their derivatives. Modern variants of the Mannich reaction that expand the potential of the classical intermolecular reaction significantly and enable efficient control of the regioselectivity and stereoselectivity are therefore the topic of intensive research. Intramolecular reactions, in particular as part of domino reaction sequences, often afford astoundingly simple and elegant approaches to complex target compounds.

Enantioselective Copper-Catalyzed Conjugate Addition and Allylic Substitution Reactions

2008-08-01

Alexandre Alexakis , J.-E. Bäckvall , Norbert Krause +2 more

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnantioselective Copper-Catalyzed Conjugate Addition and Allylic Substitution ReactionsA. Alexakis†, J. E. Bäckvall‡, N. Krause§, O. Pàmies⊥, and M. Diéguez*⊥View Author Information Departament of Organic Chemistry, University of … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnantioselective Copper-Catalyzed Conjugate Addition and Allylic Substitution ReactionsA. Alexakis†, J. E. Bäckvall‡, N. Krause§, O. Pàmies⊥, and M. Diéguez*⊥View Author Information Departament of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 Genève 4, Switzerland, Department of Organic Chemistry, Stockholm University, Arrhenius Laboratoriet, 106 91 Stockholm, Sweden, Organic Chemistry II, Dormund University of Technology, Otto-Hahn-Strasse 6, D-44227 Dortmund, Germany, and Departament de Química Física i Inorgànica, Universitat Rovira i Virgili,C/ Marcel·lí Domingo s/n, 43007 Tarragona, Spain* Corresponding author. E-mail: [email protected]†University of Geneva.‡Stockholm University.§Dormund University of Technology.⊥Universitat Rovira i Virgili.Cite this: Chem. Rev. 2008, 108, 8, 2796–2823Publication Date (Web):August 1, 2008Publication History Received14 January 2008Published online1 August 2008Published inissue 1 August 2008https://pubs.acs.org/doi/10.1021/cr0683515https://doi.org/10.1021/cr0683515review-articleACS PublicationsCopyright © 2008 American Chemical SocietyRequest reuse permissionsArticle Views21402Altmetric-Citations917LEARN 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:Enones,Ligands,Reagents,Stereoselectivity,Substitution reactions Get e-Alerts

New Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels−Alder Reaction

2000-04-15

Kateri A. Ahrendt , Christopher J. Borths , David W. C. MacMillan

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTNew Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels−Alder ReactionKateri A. Ahrendt, Christopher J. Borths, and David W. C. MacMillanView Author Information Department of Chemistry, … ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTNew Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels−Alder ReactionKateri A. Ahrendt, Christopher J. Borths, and David W. C. MacMillanView Author Information Department of Chemistry, University of California Berkeley, California 94720 Cite this: J. Am. Chem. Soc. 2000, 122, 17, 4243–4244Publication Date (Web):April 15, 2000Publication History Received7 January 2000Published online15 April 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/ja000092shttps://doi.org/10.1021/ja000092srapid-communicationACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views57345Altmetric-Citations1453LEARN 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 SUBJECTS:Amines,Catalysts,Cyclization,Ions,Stereoselectivity Get e-Alerts

Catalytic Asymmetric Organozinc Additions to Carbonyl Compounds

2001-03-01

Lin Pu , Hongbin Yu

Because of the tremendous effort of a great number of researchers, the catalytic asymmetric dialkylzinc addition to aldehydes has become a mature method. Ligands of diverse structures have been obtained, … Because of the tremendous effort of a great number of researchers, the catalytic asymmetric dialkylzinc addition to aldehydes has become a mature method. Ligands of diverse structures have been obtained, and high enantioselectivity for all different types of aldehydes have been achieved. Among the representative excellent catalysts are compounds 1, 8, 120, 325, 352, and 360 discussed above. However, compared to the well-developed dialkylzinc addition, the catalytic asymmetric reactions of aryl-, vinyl-, and alkynylzinc reagents with aldehydes are still very much under developed. Although catalysts such as (S)-402 and 210 prepared by Pu and Bolm have shown good enantioselectivity for the reaction of diphenylzinc with certain aromatic and aliphatic aldehydes, the generality of these catalysts for other [formula: see text] arylzinc reagents have not been studied. The vinylzinc additions using ligands 1 and 412 reported by Oppolzer and Wipf were highly enantioselective for certain aromatic aldehydes but not as good for aliphatic aldehydes. Carreira discovered highly enantioselective alkynylzinc additions to aldehydes promoted by the chiral amino alcohol 415, but this process was not catalytic yet. Ishizaki achieved good enantioselectivity for the catalytic alkynylzinc addition to certain aldehydes by using compounds 160, but the enantioselectivity for simple linear aliphatic aldehydes was low. Another much less explored area is the organozinc addition to ketones. Yus and Fu showed very promising results by using ligands 381 and 406 for both dialkylzinc and diphenylzinc additions to ketones, but the scope of these reactions were still very limited. Therefore, more work is needed for the aryl-, vinyl-, and alkynylzinc additions and for the organozinc addition to ketones, although many good catalysts have been obtained for the dialkylzinc addition to aldehydes. Development of these reactions will allow the catalytic asymmetric synthesis of a great variety of functional chiral alcohols that are either the structural units or synthons of many important organic molecules as well as molecules of biological functions. Macromolecular chiral catalysts have become a very attractive research subject in recent years because these materials offer the advantages of simplified product isolation, easy recovery of the generally quite expensive chiral catalysts, and potential use for continuous production. Three types of macromolecules including flexible achiral polymers anchored with chiral catalysts, rigid and sterically regular main chain chiral polymers, and chiral dendrimers have been used for the asymmetric organozinc addition to aldehydes. Among these materials, the binaphthyl-based polymers such as (R)-451 developed by Pu have shown very high and general enantioselectivity. Study of the binaphthyl polymers in the asymmetric organozinc addition has demonstrated that it is possible to systematically modify the structure and function of the rigid and sterically regular polymer for the development of highly enantioselective polymer catalysts. The catalytic properties of highly enantioselective monomer catalysts can also be preserved in the rigid and sterically regular polymer provided the catalytically active species of the monomer catalyst is not its aggregate. The TADDOL-based polymers and dendrimers prepared by Seebach showed very high and stable enantioselectivity for the diethylzinc addition to benzaldehyde even after many cycles. These studies on macromolecular chiral catalysts demonstrate that these materials are potentially very useful for practical applications.

Asymmetric Catalysis with Water: Efficient Kinetic Resolution of Terminal Epoxides by Means of Catalytic Hydrolysis

1997-08-15

Makoto Tokunaga , Jay F. Larrow , Fumitoshi Kakiuchi +1 more

Epoxides are versatile building blocks for organic synthesis. However, terminal epoxides are arguably the most important subclass of these compounds, and no general and practical method exists for their production … Epoxides are versatile building blocks for organic synthesis. However, terminal epoxides are arguably the most important subclass of these compounds, and no general and practical method exists for their production in enantiomerically pure form. Terminal epoxides are available very inexpensively as racemic mixtures, and kinetic resolution is an attractive strategy for the production of optically active epoxides, given an economical and operationally simple method. Readily accessible synthetic catalysts (chiral cobalt-based salen complexes) have been used for the efficient asymmetric hydrolysis of terminal epoxides. This process uses water as the only reagent, no added solvent, and low loadings of a recyclable catalyst (<0.5 mole percent), and it affords highly valuable terminal epoxides and 1,2-diols in high yield with high enantiomeric enrichment.

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

2005-07-23

Chao‐Jun Li

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTOrganic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade UpdateChao-Jun LiView Author Information Department of Chemistry, McGill University, 801 Sherbrooke Street West, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTOrganic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade UpdateChao-Jun LiView Author Information Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec H3A 2K6, Canada, and Department of Chemistry, Tulane University, New Orleans, Louisiana 70118 Cite this: Chem. Rev. 2005, 105, 8, 3095–3166Publication Date (Web):July 23, 2005Publication History Received31 January 2005Published online23 July 2005Published inissue 1 August 2005https://pubs.acs.org/doi/10.1021/cr030009uhttps://doi.org/10.1021/cr030009uresearch-articleACS PublicationsCopyright © 2005 American Chemical SocietyRequest reuse permissionsArticle Views24094Altmetric-Citations2064LEARN 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:Aldehydes,Anions,Catalysts,Hydrocarbons,Solvents Get e-Alerts

Nucleophilic Phosphine Organocatalysis

2004-08-01

Joey L. Methot , William Roush

Abstract Phosphines have recently become popular choices as nucleophilic catalysts in organic synthesis. The unique reactivity of phosphines compared to amines has allowed the discovery of new nucleophilic addition reactions … Abstract Phosphines have recently become popular choices as nucleophilic catalysts in organic synthesis. The unique reactivity of phosphines compared to amines has allowed the discovery of new nucleophilic addition reactions at the α‐ and γ‐positions of unsaturated carbonyl compounds, as well as novel [3+2] and [4+2] cycloaddition reactions of activated alkynes and alkenes. The accessibility of chiral phosphines has rendered several of these transformations enantioselective and has made possible the kinetic resolution of racemic secondary alcohols by phosphine‐catalyzed acylation. This mini‐review presents recent advances in nucleophilic phosphine organocatalysis for carbon‐carbon bond formation.

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Aryl−Aryl Bond Formation One Century after the Discovery of the Ullmann Reaction

2002-03-08

Jwanro Hassan , Marc Sévignon , Christel Gozzi +2 more

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAryl−Aryl Bond Formation One Century after the Discovery of the Ullmann ReactionJwanro Hassan, Marc Sévignon, Christel Gozzi, Emmanuelle Schulz, and Marc LemaireView Author Information Laboratoire de Catalyse … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAryl−Aryl Bond Formation One Century after the Discovery of the Ullmann ReactionJwanro Hassan, Marc Sévignon, Christel Gozzi, Emmanuelle Schulz, and Marc LemaireView Author Information Laboratoire de Catalyse et Synthèse Organique, UMR 5622, Université Claude Bernard Lyon 1, CPE, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex, France, and Laboratoire de Catalyse Moleculaire, UPRESA, CNRS 8075, Institut de Chimie Moléculaire d'Orsay, Université Paris-Sud, 91405 Orsay Cedex, France Cite this: Chem. Rev. 2002, 102, 5, 1359–1470Publication Date (Web):March 8, 2002Publication History Received9 July 2001Published online8 March 2002Published inissue 1 May 2002https://pubs.acs.org/doi/10.1021/cr000664rhttps://doi.org/10.1021/cr000664rresearch-articleACS PublicationsCopyright © 2002 American Chemical SocietyRequest reuse permissionsArticle Views43479Altmetric-Citations3379LEARN 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,Aromatic compounds,Catalysts,Cross coupling reaction,Reaction products Get e-Alerts

1,1‘-Binaphthyl Dimers, Oligomers, and Polymers: Molecular Recognition, Asymmetric Catalysis, and New Materials

1998-10-07

Lin Pu

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT1,1'-Binaphthyl Dimers, Oligomers, and Polymers: Molecular Recognition, Asymmetric Catalysis, and New Materials†Lin PuView Author Information Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901 Cite this: Chem. … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT1,1'-Binaphthyl Dimers, Oligomers, and Polymers: Molecular Recognition, Asymmetric Catalysis, and New Materials†Lin PuView Author Information Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901 Cite this: Chem. Rev. 1998, 98, 7, 2405–2494Publication Date (Web):October 7, 1998Publication History Received16 June 1997Revised21 August 1998Published online7 October 1998Published inissue 5 November 1998https://pubs.acs.org/doi/10.1021/cr970463whttps://doi.org/10.1021/cr970463wresearch-articleACS PublicationsCopyright © 1998 American Chemical SocietyRequest reuse permissionsArticle Views7252Altmetric-Citations1021LEARN 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,Chemical structure,Ligands,Molecules,Polymers Get e-Alerts

The advent and development of organocatalysis

2008-09-01

David W. C. MacMillan

Oxidation of α,β-un saturated aldehydes

1981-01-01

Balkrishna S. Bal , Wayne E. Childers , Harold W. Pinnick

Asymmetric Organocatalytic Domino Reactions

2007-01-16

Dieter Enders , Christoph Grondal , Matthias R. M. Hüttl

The current status of organic synthesis is hampered by costly protecting-group strategies and lengthy purification procedures after each synthetic step. To circumvent these problems, the synthetic potential of multicomponent domino … The current status of organic synthesis is hampered by costly protecting-group strategies and lengthy purification procedures after each synthetic step. To circumvent these problems, the synthetic potential of multicomponent domino reactions has been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process. In particular, domino reactions mediated by organocatalysts are in a way biomimetic, as this principle is used very efficiently in the biosynthesis of complex natural products starting from simple precursors. In this Minireview, we discuss the current development of this fast-growing field.

Isatins As Privileged Molecules in Design and Synthesis of Spiro-Fused Cyclic Frameworks

2012-09-06

Girija S. Singh , Zelalem Yibralign Desta

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTIsatins As Privileged Molecules in Design and Synthesis of Spiro-Fused Cyclic FrameworksGirija S. Singh*† and Zelalem Y. Desta†View Author Information† Chemistry Department, University of Botswana, Private Bag: … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTIsatins As Privileged Molecules in Design and Synthesis of Spiro-Fused Cyclic FrameworksGirija S. Singh*† and Zelalem Y. Desta†View Author Information† Chemistry Department, University of Botswana, Private Bag: 0022, Gaborone, Botswana*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 11, 6104–6155Publication Date (Web):September 6, 2012Publication History Received30 March 2012Published online6 September 2012Published inissue 14 November 2012https://pubs.acs.org/doi/10.1021/cr300135yhttps://doi.org/10.1021/cr300135yreview-articleACS PublicationsCopyright © 2012 American Chemical SocietyRequest reuse permissionsArticle Views18671Altmetric-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:Addition reactions,Catalysts,Chemical reactions,Cyclization,Stereoselectivity Get e-Alerts

Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the Asymmetric Michael Reaction of Aldehydes and Nitroalkenes

2005-06-01

Yujiro Hayashi , Hiroaki Gotoh , Takaaki Hayashi +1 more

The direct, catalytic, asymmetric Michael addition of aldehydes to nitroolefins in the presence of a chiral diphenylprolinol silyl ether organocatalyst is described (see scheme). The desired 1,4-addition products were obtained … The direct, catalytic, asymmetric Michael addition of aldehydes to nitroolefins in the presence of a chiral diphenylprolinol silyl ether organocatalyst is described (see scheme). The desired 1,4-addition products were obtained in nearly optically pure form in good yield with high syn diastereoselectivity. TMS=trimethylsilyl. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z500599_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Catalytic Asymmetric Dearomatization Reactions

2012-12-03

Chun‐Xiang Zhuo , Wei Zhang , Shu‐Li You

This Review summarizes the development of catalytic asymmetric dearomatization (CADA) reactions. The CADA reactions discussed herein include oxidative dearomatization reactions, dearomatization by Diels-Alder and related reactions, the alkylative dearomatization of … This Review summarizes the development of catalytic asymmetric dearomatization (CADA) reactions. The CADA reactions discussed herein include oxidative dearomatization reactions, dearomatization by Diels-Alder and related reactions, the alkylative dearomatization of electron-rich arenes, transition-metal-catalyzed dearomatization reactions, cascade sequences involving asymmetric dearomatization as the key step, and nucleophilic dearomatization reactions of pyridinium derivatives. Asymmetric dearomatization reactions with chiral auxiliaries and catalytic asymmetric reactions of dearomatized substrates are also briefly introduced. This Review intends to provide a concept for catalytic asymmetric dearomatization.

Chiral Bis(oxazoline) Copper(II) Complexes: Versatile Catalysts for Enantioselective Cycloaddition, Aldol, Michael, and Carbonyl Ene Reactions

2000-01-19

Jeffrey S. Johnson , David A. Evans

A bis(oxazoline) (box) copper(II) complex and its hydrated counterpart (1 and 2) function as enantioselective Lewis acid catalysts for carbocyclic and hetero Diels−Alder, aldol, Michael, ene, and amination reactions with … A bis(oxazoline) (box) copper(II) complex and its hydrated counterpart (1 and 2) function as enantioselective Lewis acid catalysts for carbocyclic and hetero Diels−Alder, aldol, Michael, ene, and amination reactions with substrates capable of chelation through six- and five-membered rings. X-ray crystallography of the chiral complexes reveals a propensity for the formation of distorted square planar or square pyramidal geometries. The sense of asymmetric induction is identical for all the processes catalyzed by [Cu((S,S)-t-Bu-box)](X)2 complexes 1 and 2 (X = OTf and SbF) resulting from the intervention of a distorted square planar catalyst-substrate binary complex. These catalyzed processes exhibit excellent temperature−selectivity profiles. Reactions catalyzed by [Cu(S,S-Ph-pybox)](SbF6)2 and their derived chelation complexes are also discussed.

Enantioselective Addition of Organometallic Reagents to Carbonyl Compounds: Chirality Transfer, Multiplication, and Amplification

1991-01-01

Ryōji Noyori , Masato Kitamura

Abstract Nucleophilic addition of organometallic reagents to carbonyl substrates constitutes one of the most fundamental operations in organic synthesis. Modification of the organometallic compounds by chiral, nonracemic auxiliaries offers a … Abstract Nucleophilic addition of organometallic reagents to carbonyl substrates constitutes one of the most fundamental operations in organic synthesis. Modification of the organometallic compounds by chiral, nonracemic auxiliaries offers a general opportunity to create optically active alcohols, and the catalytic version in particular provides maximum synthetic efficiency. The use of organozinc chemistry, unlike conventional organolithium or ‐magnesium chemistry, has realized an ideal catalytic enantioselective alkylation of aldehydes leading to a diverse array of secondary alcohols of high optical purity. A combination of dialkylzinc compounds and certain sterically constrained β‐dialkylamino alcohols, such as (–)‐3‐ exo ‐dimethylaminoiso‐ borneol [(–)‐DAIB], as chiral inducers affords the best result (up to 99% ee ). The alkyl transfer reaction occurs via a dinuclear Zn complex containing a chiral amino alkoxide, an aldehyde ligand, and three alkyl groups. The chiral multiplication method exhibits enormous chiral amplification: a high level of enantioselection (up to 98%) is attainable by use of DAIB in 14% ee . This unusual nonlinear effect is a result of a marked difference in chemical properties of the diastereomeric (homochiral and heterochiral) dinuclear complexes formed from the dialkylzinc and the DAIB auxiliary. This phenomenon may be the beginning of a new generation of enantioselective organic reactions.

Catalytic Enantioselective Diels-Alder Reactions: Methods, Mechanistic Fundamentals, Pathways, and Applications

2002-05-17

E. J. Corey

One hundred years after the birth of Kurt Alder and seventy-five years after the discovery of his famous reaction, one of the most important and fascinating transformations in chemistry, research … One hundred years after the birth of Kurt Alder and seventy-five years after the discovery of his famous reaction, one of the most important and fascinating transformations in chemistry, research on that process continues to surprise, excite, delight, and inform the chemical community. This article is based on presentations given first at the University of Cologne, Germany (Kurt Alder lecture, 1992), then at the Roger Adams Award Symposium (1993), and later at the Bürgenstock Conference of 2001, and describes research by our group on the development and understanding of enantioselective versions of the Diels–Alder reactions. The elements of this review include 1) development of new chiral Lewis acid catalysts for highly enantioselective (>25:1) [4+2] cycloadditions; 2) the fine mechanistic details and pre-transition-state assemblies of these reactions; 3) the fundamental understanding of catalytic activity and enantioselectivity for highly enantioselective Diels–Alder processes; and 4) applications to the synthesis of complex molecules. The range and power of the Diels–Alder reaction have steadily increased over seven decades. The end of this remarkable development is not in sight, a high compliment to this field of Science and to its great inventor.

Enamine-Based Organocatalysis with Proline and Diamines: The Development of Direct Catalytic Asymmetric Aldol, Mannich, Michael, and Diels−Alder Reactions

2004-07-10

Wolfgang Notz , Fujie Tanaka , Carlos F. Barbas

Enamines and imines have long been recognized as key intermediates in enzyme catalysis, particularly within a class of enzymes organic chemists would very much like to emulate, the aldolases. Here … Enamines and imines have long been recognized as key intermediates in enzyme catalysis, particularly within a class of enzymes organic chemists would very much like to emulate, the aldolases. Here we summarize the contributions of this laboratory to converting enzymatic enamines, and in some cases imines, into a versatile catalytic asymmetric strategy powered by small organic molecules.

Pyrrole, pyrrolidine, pyridine, piperidine and tropane alkaloids (1998 to 1999)

2000-01-01

David O′Hagan

Covering 1998–1999 with selected references from 1997. Previous review: 1997, 14, 637. Covering 1998–1999 with selected references from 1997. Previous review: 1997, 14, 637.

Asymmetric Ion‐Pairing Catalysis

2012-11-28

Katrien Brak , Eric N. Jacobsen

Charged intermediates and reagents are ubiquitous in organic transformations. The interaction of these ionic species with chiral neutral, anionic, or cationic small molecules has emerged as a powerful strategy for … Charged intermediates and reagents are ubiquitous in organic transformations. The interaction of these ionic species with chiral neutral, anionic, or cationic small molecules has emerged as a powerful strategy for catalytic, enantioselective synthesis. This review describes developments in the burgeoning field of asymmetric ion-pairing catalysis with an emphasis on the insights that have been gleaned into the structural and mechanistic features that contribute to high asymmetric induction.

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Effect of Chlorpromazine or Haloperidol on Formation of 3‐Methoxytyramine and Normetanephrine in Mouse Brain

1963-09-01

Arvid Carlsson , Margit Lindqvist

Asymmetric Organocatalysis: From Infancy to Adolescence

2008-04-17

Alessandro Dondoni , Alessandro Massi

After an initial period of validating asymmetric organocatalysis by using a wide range of important model reactions that constitute the essential tools of organic synthesis, the time has now been … After an initial period of validating asymmetric organocatalysis by using a wide range of important model reactions that constitute the essential tools of organic synthesis, the time has now been reached when organocatalysis can be used to address specific issues and solve pending problems of stereochemical relevance. This Review deals with selected studies reported in 2006 and the first half of 2007, and is intended to highlight four main aspects that may be taken as testimony of the present status and prospective of organocatalysis: a) chemical efficiency; b) discovery of new substrate combinations to give new asymmetric syntheses; c) development of new catalysts for specific purposes by using mechanistic findings; and d) applications of organocatalytic reactions in the asymmetric total synthesis of target natural products and known compounds of biological and pharmaceutical relevance.

Chiral Brønsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation

2004-04-09

Daisuke Uraguchi , Masahiro Terada

It was found that the phosphoric acid derivatives of general structure 1 serve as highly effective catalysts for the direct addition of acetyl acetone to N-Boc-protected arylimines. The beneficial effects … It was found that the phosphoric acid derivatives of general structure 1 serve as highly effective catalysts for the direct addition of acetyl acetone to N-Boc-protected arylimines. The beneficial effects of the 3,3'-bisaryl substituents of the catalysts on the enantioselectivity are greatly appreciated, and thus 1d functions as an excellent catalyst. The Brønsted acid-catalyzed direct Mannich reactions presented herein provide an attractive way to construct beta-aminoketones under extremely mild conditions. The stereochemical course of this reaction was established through the synthesis of Boc-(S)-phenylglycine methylester. The transformation thus demonstrated is applicable to a useful method for the synthesis of various phenylglycine derivatives.

Pot economy and one-pot synthesis

2016-01-01

Yujiro Hayashi

This review describes the importance and usefulness of pot-economy and one-pot reactions in current synthetic organic chemistry. This review describes the importance and usefulness of pot-economy and one-pot reactions in current synthetic organic chemistry.

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Enantioselective addition of organozinc reagents to aldehydes

1992-07-01

Kenso Soai , Seiji Niwa

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEnantioselective addition of organozinc reagents to aldehydesKenso Soai and Seiji NiwaCite this: Chem. Rev. 1992, 92, 5, 833–856Publication Date (Print):July 1, 1992Publication History Published online1 May 2002Published … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEnantioselective addition of organozinc reagents to aldehydesKenso Soai and Seiji NiwaCite this: Chem. Rev. 1992, 92, 5, 833–856Publication Date (Print):July 1, 1992Publication History Published online1 May 2002Published inissue 1 July 1992https://pubs.acs.org/doi/10.1021/cr00013a004https://doi.org/10.1021/cr00013a004research-articleACS PublicationsRequest reuse permissionsArticle Views5280Altmetric-Citations1172LEARN 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

Domino Reactions in Organic Synthesis

1996-01-01

Lutz F. Tietze

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDomino Reactions in Organic SynthesisLutz F. TietzeView Author Information Institute of Organic Chemistry of the Georg-August-Universität, Tammannstrasse 2, D-37077 Göttingen, Germany Cite this: Chem. Rev. 1996, 96, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDomino Reactions in Organic SynthesisLutz F. TietzeView Author Information Institute of Organic Chemistry of the Georg-August-Universität, Tammannstrasse 2, D-37077 Göttingen, Germany Cite this: Chem. Rev. 1996, 96, 1, 115–136Publication Date (Web):February 1, 1996Publication History Received31 August 1995Revised17 November 1995Published online1 February 1996Published inissue 1 January 1996https://pubs.acs.org/doi/10.1021/cr950027ehttps://doi.org/10.1021/cr950027eresearch-articleACS PublicationsCopyright © 1996 American Chemical SocietyRequest reuse permissionsArticle Views25483Altmetric-Citations3677LEARN 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,Aldehydes,Chemical reactions,Cyclization,Ethers Get e-Alerts

Iminium Catalysis

2007-12-01

A. Erkkilä , Inkeri Majander , Petri M. Pihko

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIminium CatalysisAnniina Erkkilä, Inkeri Majander, and Petri M. PihkoView Author Information Laboratory of Organic Chemistry, Department of Chemical Technology, Helsinki University of Technology, P.O. Box 6100, FI-02015 … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIminium CatalysisAnniina Erkkilä, Inkeri Majander, and Petri M. PihkoView Author Information Laboratory of Organic Chemistry, Department of Chemical Technology, Helsinki University of Technology, P.O. Box 6100, FI-02015 TKK, Finland Cite this: Chem. Rev. 2007, 107, 12, 5416–5470Publication Date (Web):December 12, 2007Publication History Received7 May 2007Published online12 December 2007Published inissue 1 December 2007https://doi.org/10.1021/cr068388pCopyright © 2007 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views27300Altmetric-Citations1227LEARN 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:Addition reactions,Catalysts,Conjugate acid-base pairs,Enones,Stereoselectivity Get e-Alerts

Enantioselective Organocatalysis

2001-10-15

Peter I. Dalko , Lionel Moisan

The last few years have witnessed a spectacular advancement in new catalytic methods based on metal-free organic molecules. In many cases, these small compounds give rise to extremely high enantioselectivities. … The last few years have witnessed a spectacular advancement in new catalytic methods based on metal-free organic molecules. In many cases, these small compounds give rise to extremely high enantioselectivities. Preparative advantages are notable: usually the reactions can be performed under an aerobic atmosphere with wet solvents. The catalysts are inexpensive and they are often more stable than enzymes or other bioorganic catalysts. Also, these small organic molecules can be anchored to a solid support and reused more conveniently than organometallic/bioorganic analogues, and show promising adaptability to high-throughput screening and process chemistry. Herein we focus on four different domains in which organocatalysis has made major advances: 1) The activation of the reaction based on the nucleophilic/electrophilic properties of the catalysts. This type of catalysis has much in common with conventional Lewis acid/base activation by metal complexes. 2) Transformations in which the organic catalyst forms a reactive intermediate: the chiral catalyst is consumed in the reaction and requires regeneration in a parallel catalytic cycle. 3) Phase-transfer reactions: The chiral catalyst forms a host–guest complex with the substrate and shuttles between the standard organic solvent and the second phase (i.e. a solid, aqueous, or fluorous phase in which the organic transformation takes place). 4) Molecular-cavity-accelerated asymmetric transformations: the catalyst can select between competing substrates, depending on size and structure criteria. The rate acceleration of a given reaction is similar to the Lewis acid/base activation and is the consequence of the simultaneous action of different polar functions. Herein it is shown that organocatalysis complements rather than competes with current methods. It offers something conceptually novel and opens new horizons in synthesis.

Asymmetric organocatalysis

2005-01-01

Jayasree Seayad , Benjamin List

The field of asymmetric organocatalysis is rapidly developing and attracts an increasing number of research groups around the world. Here we present a brief overview of this area, guided by … The field of asymmetric organocatalysis is rapidly developing and attracts an increasing number of research groups around the world. Here we present a brief overview of this area, guided by a mechanistic classification. Accordingly, organocatalysts are categorized as either Lewis base, Lewis acid, Brønsted base, or Brønsted acid catalysts.

Organocatalytic Enantioselective Access to Phosphorus(V) Stereocenters

2025-06-23

| Synfacts

Diastereoselective Synthesis of Silyl-Substituted Pyrrolidines

2025-06-21

Davide Carboni , Giulio Casagranda , Simone Di Remigio +3 more | The Journal of Organic Chemistry

In this paper, we report the synthesis and structural investigation of enantioenriched methylene isosteres of Hayashi-Jørgensen catalysts, and their application in organocatalysis. N-protected pyrrolidines 7b-d were prepared in high yields … In this paper, we report the synthesis and structural investigation of enantioenriched methylene isosteres of Hayashi-Jørgensen catalysts, and their application in organocatalysis. N-protected pyrrolidines 7b-d were prepared in high yields and excellent diastereoselectivity using a new one-pot, four-step synthetic protocol involving: (a) the formation of a silyllithium reagent (1), (b) its addition to a diaryl olefin (2) to generate a silyl-substituted diphenylethyllithium intermediate (3), (c) the highly diastereoselective addition of this intermediate to a chiral sulfinimine (4), and (d) intramolecular cyclization to the desired products. After N-deprotection, the new catalysts 8 were further evaluated in benchmark Michael additions of aliphatic aldehydes to β-nitrostyrene, under various conditions, demonstrating reactivity and stereoselectivity comparable to the Hayashi catalyst. Notably, the trimethylsilyl derivative (S)-8d showed superior enantioselectivity, transferring its stereochemical information with remarkable efficiency (up to 99% ee). Structural studies through 2D-NMR and DFT calculations revealed different conformational preferences for the corresponding enamines, providing insight into the observed catalytic performance.

Synthesis of Bisindoles via Oxidative Cleavage of 1,2-Diols Using Periodic Acid

2025-06-19

Ankusab Noorahmadsab Nadaf , Narasashetty Jagadish Babu | Current Catalysis

Background: Many important drugs contain a class of preferred motifs called bi-sindoles. The development of synthetic approaches for bis(indolyl)methanes (BIMs) offers numerous advantages. However, most methods for synthesizing BIM derivatives … Background: Many important drugs contain a class of preferred motifs called bi-sindoles. The development of synthetic approaches for bis(indolyl)methanes (BIMs) offers numerous advantages. However, most methods for synthesizing BIM derivatives require metal catalysts. Aims: This study aimed to synthesize bisindoles via oxidative cleavage of 1,2-diols using pe-riodic. acid. Methods: For the synthesis of bisindoles via oxidative cleavage of 1,2-diols, periodic acid was used. It is a gentle, reasonably priced, and effective testing agent for the synthesis of bi-sindole analogs from a range of 1,2-diols. Aldehydes were produced by the in situ oxidation of 1,2-diols by periodic acid, and they reacted with indoles to generate a range of bisindoles. The HIO3 generated in situ from periodic acid accelerated the reaction. The structures of the compounds were confirmed by NMR (1H and 13C), high-resolution mass spectrometry (HRMS), and elemental analysis using a CHNS analyzer. Results: A variety of BIMs derivatives were produced by oxidatively breaking down 1,2-diols using periodic acid. The appealing aspects of this procedure include its high yield, rap-id response time, and catalyst-free conditions. Conclusion: In this study, a productive and sustainable method for creating BIMs deriva-tives is presented. The procedure is genuinely green since it uses periodic acid as an oxidiz-ing agent rather than a conventional catalyst, has a clean reaction profile, quick reaction times, and is inexpensive.

Mercaptan-free approach to the synthesis of Ethiprole, an insecticide

2025-06-18

Rachel Gundamalla , P. Naveen Reddy , RajashakerBantu +1 more | Tetrahedron Letters

Palladium(0)-Catalyzed Asymmetric Cross Inverse-Electron-Demand Diels–Alder Reaction between Distinct Electron-Deficient Dienes

2025-06-18

Ke Xie , Bao-Rui Kong , C. Wang +3 more | Organic Letters

Here we present an asymmetric and regioselective cross inverse-electron-demand Diels-Alder reaction between 2,4-dienyl carbonyls and 1-heterodienes or allylidenemalononitriles, by reversing the reactivity of the former electrophilic partners via γ,δ-dihapto coordination … Here we present an asymmetric and regioselective cross inverse-electron-demand Diels-Alder reaction between 2,4-dienyl carbonyls and 1-heterodienes or allylidenemalononitriles, by reversing the reactivity of the former electrophilic partners via γ,δ-dihapto coordination with palladium(0) and backdonation. A broad spectrum of multifunctional tetrahydropyridines, dihydropyrans and cyclohexene derivatives are generally constructed in high yields, diastereo- and enantioselectivity, even with low catalyst loadings (0.6 mol % of Pd).

Aggregation‐Induced Asymmetric Synthesis of 2,3‐Dihydrobenzofurans by [4 + 1] Annulation with Substituted Salicyl N‐Phosphonyl Imines

2025-06-17

Guigen Li , Qingkai Yuan , Jun Yan +5 more | European Journal of Organic Chemistry

The aggregation‐induced asymmetric synthesis of trans‐2,3‐dihydrobenzofuran compounds was achieved via the reaction of salicyl N‐phosphonyl imines with sulfur ylide. This transformation proceeds through a [4 + 1] annulation pathway, affording … The aggregation‐induced asymmetric synthesis of trans‐2,3‐dihydrobenzofuran compounds was achieved via the reaction of salicyl N‐phosphonyl imines with sulfur ylide. This transformation proceeds through a [4 + 1] annulation pathway, affording products in good to excellent yields with tunable diastereoselectivities. By employing various THF/EtOH cosolvent systems in conjunction with group‐assisted purification (GAP) chemistry, the conventional aggregation cosolvent systems were shown to play a crucial role in enhancing diastereoselectivity and modulating aggregate formation. This was supported by studies involving aggregation‐induced emission (AIE), aggregation‐induced polarization (AIP), and dynamic light scattering (DLS). The developed protocol provides a practical and versatile synthetic approach to 2,3‐dihydrobenzofuran scaffolds, highlighting the utility of aggregation‐induced asymmetric synthesis (AIAS) as a powerful strategy for achieving stereocontrol.

Development of a Vinylated Cyclic Allene: A Fleeting Strained Diene for the Diels‐Alder Reaction

2025-06-17

Haruki Mizoguchi , T. Obata , T. Hirai +2 more | Angewandte Chemie

Fleeting molecules possessing strained multiple bonds are important components in organic synthesis due to their ability to undergo various chemical reactions driven by the release of strain energy. While the … Fleeting molecules possessing strained multiple bonds are important components in organic synthesis due to their ability to undergo various chemical reactions driven by the release of strain energy. While the use of strained π‐bonds as 2π components, represented by dienophiles in Diels‐Alder reactions, has been well studied, “the strained diene (4π component) approach” for molecular construction remains underexplored. Herein, we report the design of a vinyl cyclic allene (1‐vinyl‐1,2‐cyclohexadiene) as a highly reactive strained diene and the development of its Diels‐Alder reactions. Experimental and computational studies of vinyl cyclic allenes revealed that this diene system undergoes cycloaddition with dienophiles regio‐ and stereoselectively under mild reaction conditions. These studies also provide insight into the reactivity and selectivity of the system. The strained diene approach enables the convergent construction of polycyclic molecules through bond disconnections distinct from conventional retrosynthetic analysis, thus offering an efficient strategy for the assembly of functional molecules.

Divergent Annulations via Organocatalysis: Remote-Controlled and Switchable Reactions of Pyrrolidinone-Based Morita–Baylis–Hillman Carbonates with 2-Arylideneindane-1,3-diones

2025-06-17

Rongzhen Li , Xuling Chen , Pengfei Li | Organic Letters

Developing versatile synthons for diversity-oriented synthesis is of great interest, and the switchable divergent transformations of these synthons pose a challenging task. Herein, we report the first organocatalytic remote-controlled divergent … Developing versatile synthons for diversity-oriented synthesis is of great interest, and the switchable divergent transformations of these synthons pose a challenging task. Herein, we report the first organocatalytic remote-controlled divergent annulations of pyrrolidinone-based Morita-Baylis-Hillman carbonates with 2-arylideneindane-1,3-diones. Through precise catalyst control, this transformative platform enables selective access to distinct spirocyclic architectures: 4-dimethylaminopyridine catalysis orchestrates a formal (5 + 2)-annulation between Cβ and Cε, delivering structurally complex spiro[cyclohepta[c]pyrrole-6,2'-indene]-8-carboxylates, while PPh3 catalysis redirects the reaction pathway toward a unprecedented (3 + 2)-annulation between Cε and Cε', generating synthetically valuable (spiro[cyclopenta[b]pyrrole-6,2'-inden]-3-yl)acrylates. This dual catalytic system not only expands the synthetic utility of MBH carbonates via remote control but also establishes a versatile method for accessing structurally diverse spiroheterocycles.

Formal [3 + 2] Annulation of β,β-Disubstituted Enesulfinamides with Vinyl Thianthrenium Salt: Asymmetric Construction of 3,3-Disubstituted 1-Pyrrolines

2025-06-15

S.‐P. HUANG , Chong‐Dao Lu | Organic Letters

Five-membered endocyclic imines featuring a quaternary carbon stereocenter at the α position of the imino group can be stereoselectively synthesized through the formal [3 + 2] annulation of β,β-disubstituted enesulfinamides … Five-membered endocyclic imines featuring a quaternary carbon stereocenter at the α position of the imino group can be stereoselectively synthesized through the formal [3 + 2] annulation of β,β-disubstituted enesulfinamides with vinyl thianthrenium salt. The deprotonated enesulfinamides undergo a nucleophilic addition to the vinyl sulfonium salt, which is followed by intramolecular cyclization, leading to the production of 3,3-disubstituted 1-pyrroline derivatives with high enantioselectivity. The stereochemistry of the resulting products is influenced by both the geometric configuration of the enesulfinamides and the absolute configuration of their sulfinyl group.

Highly Regio- and Diastereoselective 1,3-DC Reaction of BDAs and Nitrones: Synthesis of the Spiro[benzofuran-2,5′-isoxazolidine] Framework

2025-06-13

Shuhong Wang , W. Xie , Chaoyang Jiang +3 more | The Journal of Organic Chemistry

A novel series of spiro[benzofuran-2,5'-isoxazolidine] compounds was successfully synthesized using a catalyst-free 1,3-DC reaction between benzofuran-derived azadienes (BDAs) and nitrones. This methodology achieved high regio- and diastereoselectivity and demonstrated remarkable … A novel series of spiro[benzofuran-2,5'-isoxazolidine] compounds was successfully synthesized using a catalyst-free 1,3-DC reaction between benzofuran-derived azadienes (BDAs) and nitrones. This methodology achieved high regio- and diastereoselectivity and demonstrated remarkable tolerance toward various functional groups in both BDAs and nitrones, yielding products with good to excellent efficiencies (79-99%). Gram-scale synthesis and subsequent functional transformations further validated the application value of this method for further functionalization.

Phosphine-Catalyzed Asymmetric Dearomative Annulation of 4-Nitroisoxazoles with Allenoates: Construction of Isoxazoline-Fused Bicyclo[3.3.0]octenes

2025-06-13

Huamin Wang , Han Xie , Jianhua Ding +3 more | Organic Letters

An intermolecular phosphine-catalyzed dearomatization reaction of 4-nitroisoxazoles with allenoates was realized through one-pot sequential [3 + 2]/[3 + 2] annulation. Various isoxazoline-fused bicyclo[3.3.0]octene derivatives were successfully synthesized in good to … An intermolecular phosphine-catalyzed dearomatization reaction of 4-nitroisoxazoles with allenoates was realized through one-pot sequential [3 + 2]/[3 + 2] annulation. Various isoxazoline-fused bicyclo[3.3.0]octene derivatives were successfully synthesized in good to excellent yields (up to 98%). Under catalysis with SadPhos P7, enantioselective dearomative cyclization occurred, initiating the subsequent [3 + 2] cycloaddition process to afford valuable optically active cyclopentane-fused polycyclic scaffolds bearing a quaternary carbon stereocenter in 58-98% yields with 70-97% ee. The synthetic utility of this protocol was demonstrated by the gram-scale reaction and versatile transformations of the product.

Reactions of Aldehydes and Ketones and Their Derivatives

2025-06-13

M. G. Moloney | Organic Reaction Mechanisms/Organic reaction mechanisms

Accessing carbon, boron and germanium spiro stereocentres in a unified catalytic enantioselective approach

2025-06-12

Yi-Xuan Cao , Anne‐Sophie Chauvin , Shuo Tong +2 more | Nature Catalysis

Abstract Achieving substrate generality in asymmetric catalysis remains a long-standing goal, particularly for the selective construction of chiral heteroatoms. Compared with carbon, sulfur, phosphorus and silicon stereogenic centres, methods for … Abstract Achieving substrate generality in asymmetric catalysis remains a long-standing goal, particularly for the selective construction of chiral heteroatoms. Compared with carbon, sulfur, phosphorus and silicon stereogenic centres, methods for the construction of their boron and germanium congeners remain very scarce. Chiral (hetero) spirocycles are of relevance in several research domains. Methods effective for constructing carbon-centred chiral spirocycles do not translate to boron and germanium, leaving these chiral centres unexplored. We describe a unified strategy for constructing carbon, boron and germanium-centred chiral spirocyclic skeletons via enantioselective hetero [2+2+2] cycloaddition of a bis-alkyne with a nitrile. A chiral designer Ni(0) N -heterocyclic carbene complex enables the required long-range enantioinduction. The resulting enantio-enriched spirocycles feature a pyridine motif, making them exploitable for ligand design and functional materials featuring attractive photophysical and chiroptical properties.

Catalytic Asymmetric Synthesis of α-Allyl α-Tertiary Aminoesters from α-Iminoesters and “Umpoled” π-Allyl Co Nucleophiles

2025-06-12

Zhen Li , Ka Lu , Shu-Hua Long +6 more | ACS Catalysis

An Efficient Semipinacol Rearrangement toward α,β-Unsaturated Ketones via Lewis Acid and Base Synergistic Catalysis

2025-06-12

Jun Tan , Chengyan Xie , Nasier Yusuipujiang +3 more | The Journal of Organic Chemistry

An efficient semipinacol rearrangement undergoing 1,2-migration toward α,β-unsaturated ketones via a synergistic Lewis acid and base cocatalysis strategy is developed, providing a direct and efficient access to diverse and valuable … An efficient semipinacol rearrangement undergoing 1,2-migration toward α,β-unsaturated ketones via a synergistic Lewis acid and base cocatalysis strategy is developed, providing a direct and efficient access to diverse and valuable 1,4-dicarbonyl compounds bearing α-stereocenters with high atom economy, in which the catalytic base has played an essential role for the expected reactivity. Benefited from this method, a series of semipinacol rearrangement that otherwise could not be realized from previous reports could be successfully achieved, including the 1,2-aryl migration and 1,2-cycloalkyl migration overcoming the limitation of strained ring and rearomatization, thus bringing more opportunity for the practical application of related 1,4-dicarbonyl compounds. Classical substrate scope studies disclose the regularity on migration sequence. Further mechanistic studies confirm the 1,2-migration mechanism and give comprehensive insights for this transformation.

Asymmetric Allylboration of α-Alkoxy-enones: Access to Enantioenriched Tertiary α-Hydroxy Ketones

2025-06-11

Colton E. Johnson , Lukas J. Glofcheskie , Mark Lautens | Organic Letters

We report an organocatalyzed asymmetric allylboration of α-alkoxy enones to access α-hydroxy enol ethers in yields up to 98% and up to 99% ee. These products can be subsequently transformed … We report an organocatalyzed asymmetric allylboration of α-alkoxy enones to access α-hydroxy enol ethers in yields up to 98% and up to 99% ee. These products can be subsequently transformed into a wide range of highly oxygenated products such as α-hydroxy ketones, α-hydroxy enones, and γ-hydroxy vinylogous esters. This methodology is also applicable to other α-heteroatom-containing ketones in analogous yield and ee (99% yield and 98% ee, respectively).

Asymmetric Synthesis of Either Enantiomer of β-Butadienyl Amines by Isoprenylation of Davis–Ellman Imines

2025-06-07

Leleti Rajender Reddy , Venu Aili , Shiva Kumar Koppula | The Journal of Organic Chemistry

The asymmetric synthesis of either enantiomer of β-butadienyl amines from a single starting material is described. Reversal of the diastereoselectivity is achieved by simply tuning the reaction conditions. This methodology … The asymmetric synthesis of either enantiomer of β-butadienyl amines from a single starting material is described. Reversal of the diastereoselectivity is achieved by simply tuning the reaction conditions. This methodology provides excellent yields (up to 98%) and high diastereomeric ratios (dr up to 98:2) and exhibits a broad substrate scope.

Principles, Applications, and Advances of Organic Reaction Mechanisms

2025-06-04

| IGI Global eBooks

Chiral Phosphoric Acid-Catalyzed Enantioselective Pictet–Spengler Reaction for Concise Synthesis of CF3-Substituted Tetrahydro-β-Carbolines

2025-06-03

Shigenobu Umemiya , Susheel J. Nara , Masahiro Terada | Organic Letters

Fluorine-containing compounds are widely found in pharmaceuticals, agrochemicals, and functional materials. In particular, compounds containing enantioenriched trifluoromethyl groups are essential because they show metabolic stability, lipophilicity, and membrane permeability in … Fluorine-containing compounds are widely found in pharmaceuticals, agrochemicals, and functional materials. In particular, compounds containing enantioenriched trifluoromethyl groups are essential because they show metabolic stability, lipophilicity, and membrane permeability in vivo. In this study, an enantioselective Pictet-Spengler reaction of tryptamine derivatives with 1,1,1-trifluoro-4-[tris(1-methylethyl)silyl]-3-butyn-2-one catalyzed by a chiral phosphoric acid is demonstrated, which provides CF3-containing chiral tetrahydro-β-carboline derivatives in good yields with high enantioselectivities.

Haloindole Carboxaldehyde as an Emerging Precursor for the Synthesis of Versatile Essential Skeletons

2025-06-01

S. R. Roy , Debu Ghorai , Arunima Mukherjee +5 more | ChemistrySelect

Abstract Indole‐fused heterocycle frameworks have an extensive range of innumerable attributes. Among them, haloindole carboxaldehydes are versatile compounds widely used in organic synthesis. They serve as key intermediates in the … Abstract Indole‐fused heterocycle frameworks have an extensive range of innumerable attributes. Among them, haloindole carboxaldehydes are versatile compounds widely used in organic synthesis. They serve as key intermediates in the development of heterocycles and biologically active molecules. Because of their broad reactivity, these compounds are valuable assets in synthetic chemistry and are significantly utilized in fields such as drug discovery and pharmaceutical research. Many natural products with indole scaffolds have drug‐like properties and act as antifungal, antibacterial, antioxidant, and anticancer agents. Haloindole carbaldehydes have been used as a starting material to synthesize the potentially active indole frameworks. In this review, we have outlined a variety of methodologies to synthesize several haloindole carbaldehydes and the synthetic application to synthesize natural products and core skeletons during the last two decades. Synthetic applications of haloindole carbaldehydes have been divided in four distinct categories and each category has been further subdivided for better understanding.

Organocatalytic asymmetric umpolung reaction of cyanoketimines with 2-(bromomethyl)acrylate

2025-06-01

Cheng Cheng , Yunlong Pan , Yuhong Gao +2 more | Tetrahedron Letters

Base-Mediated Cyclization of N-Benzyl Ketimines with Vinyl Sulfoxides: An Approach to Polysubstituted 1-Pyrrolines

2025-05-29

Tenglong Xu , Donghao Wang , Zhen Liang +4 more | The Journal of Organic Chemistry

A protocol for synthesizing polysubstituted 1-pyrrolines (3,4-dihydro-2H-pyrrole) via base-mediated [3 + 2] cycloaddition of vinyl sulfoxides with N-benzyl ketimines under mild conditions has been developed. The methodology exhibits exceptional functional … A protocol for synthesizing polysubstituted 1-pyrrolines (3,4-dihydro-2H-pyrrole) via base-mediated [3 + 2] cycloaddition of vinyl sulfoxides with N-benzyl ketimines under mild conditions has been developed. The methodology exhibits exceptional functional group compatibility, demonstrating applicability to both terminal and internal vinyl sulfoxide substrates. Control experiments and 1H NMR analyses have been conducted to propose a plausible reaction pathway. The synthetic value of this strategy has been further validated through successful gram-scale synthesis and subsequent transformation of the products into diverse 1-pyrrolines derivatives.

Synthesis of Unsaturated 1,6-Diketones and 1,6-Diols from Muconic Acid

2025-05-29

Andrey I Puzanov , Dmitriy N. Zakusilo , Irina А. Boyarskaya +4 more | The Journal of Organic Chemistry

Cis-,cis-muconic acid (HO2C-CH═CH-CH═CH-CO2H) reacts with arenes in Bro̷nsted superacid TfOH, affording the aromatic acylation products, unsaturated E-,E-1,6-diketones [ArOC-CH═CH-CH═CH-COAr]. These diketones are also obtained in Friedel-Crafts acylation of arenes by muconoyl … Cis-,cis-muconic acid (HO2C-CH═CH-CH═CH-CO2H) reacts with arenes in Bro̷nsted superacid TfOH, affording the aromatic acylation products, unsaturated E-,E-1,6-diketones [ArOC-CH═CH-CH═CH-COAr]. These diketones are also obtained in Friedel-Crafts acylation of arenes by muconoyl chloride. The reaction in TfOH proceeds through an intermediate formation of muconic acid O,O-diprotonated form [HO(+HO═C)-CH═CH-CH═CH-C(═OH)+OH], which was investigated experimentally by NMR and theoretically by DFT calculations. Carbonyl reduction of these 1,6-diketones with NaBH4 results in the formation of the corresponding unsaturated diastereomeric E-,E-1,6-diols [Ar(HO)CH-CH═CH-CH═CH-CH(OH)Ar]. Catalytic hydrogenation of carbon-carbon bonds in 1,6-diketones with Pd or Pt on carbon furnishes the corresponding 1,6-diketones (ArOC-CH2CH2CH2CH2-COAr). The studied reactions contribute to the development of organic synthesis on the basis of transformations of muconic acid, which is an important compound in industrial chemistry.

Recent Progress in Asymmetric Michael Additions Catalyzed by Chiral Phosphoric Acids

2025-05-29

Zhongwen He , Teck‐Peng Loh , Lingzheng Bu +2 more | ChemistrySelect

Abstract Chiral phosphoric acids (CPAs) exhibit bifunctional catalytic properties due to their unique structural features and chemical characteristics, leading to their widespread application in various common reactions. In addition, the … Abstract Chiral phosphoric acids (CPAs) exhibit bifunctional catalytic properties due to their unique structural features and chemical characteristics, leading to their widespread application in various common reactions. In addition, the Michael addition reaction holds significant importance in the field of organic chemistry, particularly among numerous reactions involving carbon–carbon and carbon–heteroatom bond forming. This minireview systematically introduced the structure and catalytic mechanism of chiral phosphoric acid and gave an overview on the development status of Michael addition catalyzed by chiral phosphoric acids, including actual Michael addition and hetero‐Michael addition (aza‐Michael addition, oxo‐Michael addition, phospha‐Michael addition, sulfa‐Michael addition).

1,4-Diaryl-1,3-butadiyne: A powerful synthon for the PhI(OAc)2 mediated synthesis of Highly substituted naphthalene via carbocyclization

2025-05-28

Subhasis Samai | Journal of Scientific Enquiry

Synthesis of Chiral Dispiro‐Indolinone‐Pyrrolidine‐Imidazolones Using (R) or (S)‐1‐(2,4‐Dimethoxyphenyl)Ethyl Amine

2025-05-28

Vladislav S. Polyakov , Alexander A. Barashkin , Yuri K. Grishin +2 more | ChemistrySelect

Abstract Chiral dispyrindolinone‐pyrrolidine‐indolinones were obtained using a four‐step synthetic sequence: (1) preparation of thioureas and 5‐arylidene‐thiohydantoins from ( R ) or ( S )‐1‐(2,4‐dimethoxyphenyl)ethylamine; (2) 1,3‐cycloaddition reaction of the chiral … Abstract Chiral dispyrindolinone‐pyrrolidine‐indolinones were obtained using a four‐step synthetic sequence: (1) preparation of thioureas and 5‐arylidene‐thiohydantoins from ( R ) or ( S )‐1‐(2,4‐dimethoxyphenyl)ethylamine; (2) 1,3‐cycloaddition reaction of the chiral 5‐arylidene‐thiohydantoins with azomethine ylide to obtain a diastereomers' mixture; (3) diastereomers separation and removing the auxiliary 1‐(2,4‐dimethoxyphenyl)ethyl group.

An asymmetric transformation of carbenium ions

2025-05-28

Pd-Catalyzed asymmetric allylic amination with isatin using a P,olefin-type chiral ligand with C–N bond axial chirality

2025-05-23

Natsume Akimoto , Kaho Takaya , Yoshio Kasashima +3 more

In this study, we implemented the P,olefin-type chiral ligand (a R )-(−)- 6 , which contains a cyclohexyl group and a cinnamoyl group on the nitrogen atom, in the Pd-catalyzed … In this study, we implemented the P,olefin-type chiral ligand (a R )-(−)- 6 , which contains a cyclohexyl group and a cinnamoyl group on the nitrogen atom, in the Pd-catalyzed asymmetric allylic amination of allylic esters with isatin derivatives 11 as nucleophiles. The reaction proceeds efficiently, yielding the products ( S )- 13 with good-to-high enantioselectivity. A scale-up reaction was also successfully conducted at a 1 mmol scale. Additionally, when malononitrile was added to the resulting product ( S )- 13a in the presence of FeCl 3 as the catalyst, the corresponding malononitrile derivative ( S )- 16 was obtained without any loss in optical purity.