Chiral Amine-Mediated Asymmetric Conjugate Additions to Vinyl Sulfones

Chiral molecules containing sulfone groups are useful intermediates and have found wide applications in organic synthesis. In this account, recent progress in the use of vinyl sulfones as Michael acceptors in the asymmetric organocatalytic conjugate addition is summarized.

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Copper-catalyzed enantioselective conjugate addition of organometallic reagents to challenging Michael acceptors

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.16.24 ◽

2020 ◽

Vol 16 ◽

pp. 212-232 ◽

Cited By ~ 1

Author(s):

Delphine Pichon ◽

Jennifer Morvan ◽

Christophe Crévisy ◽

Marc Mauduit

Keyword(s):

Natural Products ◽

Conjugate Addition ◽

Catalytic Transformation ◽

Chiral Molecules ◽

Catalytic Systems ◽

Organometallic Reagents ◽

Recent Advances ◽

Wide Range ◽

Michael Acceptors

The copper-catalyzed enantioselective conjugate addition (ECA) of organometallic nucleophiles to electron-deficient alkenes (Michael acceptors) represents an efficient and attractive methodology for providing a wide range of relevant chiral molecules. In order to increase the attractiveness of this useful catalytic transformation, some Michael acceptors bearing challenging electron-deficient functions (i.e., aldehydes, thioesters, acylimidazoles, N-acyloxazolidinones, N-acylpyrrolidinones, amides, N-acylpyrroles) were recently investigated. Remarkably, only a few chiral copper-based catalytic systems have successfully achieved the conjugate addition of different organometallic reagents to these challenging Michael acceptors, with excellent regio- and enantioselectivity. Furthermore, thanks to their easy derivatization, the resulting chiral conjugated products could be converted into various natural products. The aim of this tutorial review is to summarize recent advances accomplished in this stimulating field.

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In Search of New Approaches to Asymmetric Conjugate Addition: Screening Studies on the Use of [Zn(bpy*)X(R)] Reagents and α,β-Unsaturated Amide Michael Acceptors

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20071107 ◽

2007 ◽

Vol 72 (8) ◽

pp. 1107-1121 ◽

Cited By ~ 7

Author(s):

Alexander J. Blake ◽

Daniela Giunta ◽

Jonathan Shannon ◽

Maurizio Solinas ◽

Francesca Walzer ◽

...

Keyword(s):

Ligand Exchange ◽

Conjugate Addition ◽

Nmr Studies ◽

Conjugate Additions ◽

New Approaches ◽

Michael Acceptors ◽

Derivatives Of ◽

Moderate Yield ◽

C Nmr

Conjugate additions of [Zn(bpy*)Cl(Et)] (bpy* = 4,4'-di-tert-butyl-2,2'-bipyridine) to cyclohex-2-en-1-one are promoted by ZnMe2 in 88% ee but in moderate yield under CuI phosphoramidite catalysis. In the absence of ZnMe2 the [Zn(bpy*)Cl(Et)] is inactive indicating a Schlenk-type equilibrium. Other derivatives of [Zn(bpy*)Cl(R)] (R = Bu, 4-methylbenzyl), prepared in situ from [ZnCl(R)] and the bipyridine give low yields due to competing chloride abstraction. 13C NMR studies indicate facile organo-ligand exchange between [Zn(bpy*)(Et)2] and [Zn(bpy*)Cl2] complexes. In the presence of the bipyridine, [ZnBr(allyl)] disproportionates into [Zn(bpy*)Br2] and [Zn(bpy*)(allyl)2] species. In separate studies, simple (E)-MeCH=CHCONMeR (R = Me, OMe) α,β-unsaturated amides undergo asymmetric 1,4-addition of EtMgBr in 75-99% yield and 48-79% ee in the presence of the diphosphines JosiPhos or MeDuPhos and copper(I) sources.

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Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.11.263 ◽

2015 ◽

Vol 11 ◽

pp. 2418-2434 ◽

Cited By ~ 36

Author(s):

Thibault E Schmid ◽

Sammy Drissi-Amraoui ◽

Christophe Crévisy ◽

Olivier Baslé ◽

Marc Mauduit

Keyword(s):

Conjugate Addition ◽

Chiral Molecules ◽

Straightforward Manner ◽

Organometallic Reagents ◽

Stereogenic Centers ◽

Michael Acceptors ◽

Sequential Generation

The copper-catalyzed asymmetric conjugate addition (ACA) of nucleophiles onto polyenic Michael acceptors represents an attractive and powerful methodology for the synthesis of relevant chiral molecules, as it enables in a straightforward manner the sequential generation of two or more stereogenic centers. In the last decade, various chiral copper-based catalysts were evaluated in combination with different nucleophiles and Michael acceptors, and have unambiguously demonstrated their usefulness in the control of the regio- and enantioselectivity of the addition. The aim of this review is to report recent breakthroughs achieved in this challenging field.

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O-AcylTEMPOs, a Modified and Fundamental, but Unexplored Carboxylic Derivative: Recent Progress in Synthetic Applications

Current Organic Chemistry ◽

10.2174/1385272823666191019102511 ◽

2019 ◽

Vol 23 (19) ◽

pp. 2102-2121

Author(s):

Hiroyuki Kawafuchi ◽

Lijian Ma ◽

Md Imran Hossain ◽

Tsutomu Inokuchi

Keyword(s):

Organic Synthesis ◽

Recent Progress ◽

Knoevenagel Condensation ◽

Acid Synthesis ◽

Amino Acid Synthesis ◽

Electrophilic Amination ◽

Weinreb Amides ◽

Anionic Species ◽

Diastereoselective Addition ◽

Carbonyl Function

O-Acylated 2,2,6,6-tetramethylpiperidine-N-oxyls (abbr. O-AcylTEMPOs) are easily available and stable carboxylic derivatives, but their utility in organic synthesis is unexplored in contrast to analogues, such as the N-methoxy-N-methylamides, known as Weinreb amides. Especially, the O–N unit of the O-acylTEMPOs dictates a fairly electronwithdrawing character for the carbonyl function. This enhances the reactivity and stability of the resulting enolate ions. Accordingly, O-acylTEMPOs allow various transformations and this review encompasses seven topics: (1) Reactivity of O-acylTEMPOs towards nucleophiles and chemoselective transformations, (2) Reactivity of anionic species derived from O-acylTEMPOs, (3) E-Selective Knoevenagel condensation of acetoacetylTEMPOs and synthesis of furans, (4) Electrocyclization of 2,4-dienones derived from acetoacetic derivatives and 2-substituted enals, (5) Diastereoselective addition of amide anion to O-(2-alkenoyl)TEMPOs and β-amino acid synthesis, (6) Thermolysis of O-acylTEMPOs, and (7) Applications for Umpolung reactions using O-benzoylTEMPOs, useful for the electrophilic amination of alkenes and alkynes.

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Chiral imidazolidinones: A class of priviliged organocatalysts in stereoselective organic synthesis

Physical Sciences Reviews ◽

10.1515/psr-2018-0087 ◽

2020 ◽

Vol 5 (5) ◽

Author(s):

Laura Raimondi ◽

Chiara Faverio ◽

Monica Fiorenza Boselli

Keyword(s):

Pharmaceutical Industry ◽

Green Chemistry ◽

Organic Synthesis ◽

Catalytic Synthesis ◽

Biological Chemistry ◽

Chiral Molecules ◽

Catalytic Systems ◽

Drug Synthesis ◽

Industry Needs

AbstractChiral molecules hold a mail position in Organic and Biological Chemistry, so pharmaceutical industry needs suitable strategies for drug synthesis. Moreover, Green Chemistry procedures are increasingly required in order to avoid environment deterioration. Catalytic synthesis, in particular organocatalysis, in thus a continuously expanding field. A survey of more recent researches involving chiral imidazolidinones is here presented, with a particular focus on immobilized catalytic systems.

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Copper-Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl-N-methylimidazole Michael Acceptors: a Powerful Synthetic Platform

Angewandte Chemie ◽

10.1002/ange.201506189 ◽

2015 ◽

Vol 127 (40) ◽

pp. 11996-12000 ◽

Cited By ~ 12

Author(s):

Sammy Drissi-Amraoui ◽

Marie S. T. Morin ◽

Christophe Crévisy ◽

Olivier Baslé ◽

Renata Marcia de Figueiredo ◽

...

Keyword(s):

Conjugate Addition ◽

Michael Acceptors

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Asymmetric conjugate additions of 2-substituted benzofuran-3(2H)-ones to α,β-unsaturated ketones catalyzed by chiral copper complexes

Organic & Biomolecular Chemistry ◽

10.1039/c7ob00677b ◽

2017 ◽

Vol 15 (19) ◽

pp. 4191-4198 ◽

Cited By ~ 7

Author(s):

Haojiang Wang ◽

Yifeng Wang ◽

Cheng Zhang ◽

Yidong Jiang ◽

Mingming Chu ◽

...

Keyword(s):

Copper Complexes ◽

Conjugate Addition ◽

Conjugate Additions ◽

Unsaturated Ketones

A highly enantioselective conjugate addition of 2-substituted benzofuran-3(2H)-ones to α,β-unsaturated ketones promoted by chiral copper complexes has been developed.

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