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

2015 ◽  
Vol 11 ◽  
pp. 2418-2434 ◽  
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.

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

2020 ◽  
Vol 16 ◽  
pp. 212-232 ◽  
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.

ChemInform Abstract: Copper-Catalyzed Asymmetric Conjugate Addition of Organometallic Reagents to Extended Michael Acceptors

ChemInform ◽  
2016 ◽  
Vol 47 (12) ◽  
pp. no-no
Author(s):  
Thibault E. Schmid ◽  
Sammy Drissi-Amraoui ◽  
Christophe Crevisy ◽  
Olivier Basle ◽  
Marc Mauduit
Keyword(s):  
Conjugate Addition ◽  
Organometallic Reagents ◽  
Michael Acceptors

Chiral Amine-Mediated Asymmetric Conjugate Additions to Vinyl Sulfones

2009 ◽  
Vol 62 (9) ◽  
pp. 951 ◽  
Author(s):  
Qiang Zhu ◽  
Yixin Lu
Keyword(s):  
Organic Synthesis ◽  
Recent Progress ◽  
Conjugate Addition ◽  
Chiral Molecules ◽  
Conjugate Additions ◽  
Chiral Amine ◽  
Michael Acceptors

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.

scholarly journals Developing a Methodology for Catalytic Asymmetric Crotylation of Aldehydes

Synlett ◽  
2021 ◽  
Author(s):  
Andrei V. Malkov ◽  
Aleksandr E. Rubtsov
Keyword(s):  
Kinetic Resolution ◽  
Lewis Base ◽  
Chiral Auxiliaries ◽  
Organometallic Reagents ◽  
Total Syntheses ◽  
Base Catalysts ◽  
Homoallylic Alcohols ◽  
Stereogenic Centers ◽  
Long Time ◽  
Lewis Base Catalysts

AbstractAsymmetric crotylation has firmly earned a place among the set of valuable synthetic tools for stereoselective construction of carbon skeletons. For a long time the field was heavily dominated by reagents bearing stoichiometric chiral auxiliaries, but now catalytic methods are gradually taking center stage, and the area continues to develop rapidly. This account focuses primarily on preformed organometallic reagents based on silicon and, to some extent, boron. It narrates our endeavors to design new and efficient chiral Lewis base catalysts for the asymmetric addition of crotyl(trichloro)silanes to aldehydes. It also covers the development of a novel protocol for kinetic resolution of racemic secondary allylboronates to give enantio- and diastereomerically enriched linear homoallylic alcohols. As a separate topic, cross-crotylation of aldehydes by using enantiopure branched homoallylic alcohols as a source of crotyl groups is discussed. Finally, the synthetic credentials of the developed methodology are illustrated by total syntheses of marine natural products, in which crotylation plays a key role in setting up stereogenic centers.1 Introduction2 Pyridine N-Oxides as Lewis Base Catalysts3 Bipyridine N,N′-Dioxides as Lewis Base Catalysts4 Chiral Allylating Reagents5 Synthetic Applications6 Concluding Remarks

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

2015 ◽  
Vol 127 (40) ◽  
pp. 11996-12000 ◽  
Author(s):  
Sammy Drissi-Amraoui ◽  
Marie S. T. Morin ◽  
Christophe Crévisy ◽  
Olivier Baslé ◽  
Renata Marcia de Figueiredo ◽  
...  
Keyword(s):  
Conjugate Addition ◽  
Michael Acceptors

scholarly journals Absolute configurations of chiral molecules with multiple stereogenic centers without prior knowledge of the relative configurations: A case study of inuloxin C

Chirality ◽  
2018 ◽  
Vol 30 (11) ◽  
pp. 1206-1214 ◽  
Author(s):  
Jordan L. Johnson ◽  
Vijay Raghavan ◽  
Alessio Cimmino ◽  
Arash Moeini ◽  
Ana G. Petrovic ◽  
...  
Keyword(s):  
Prior Knowledge ◽  
Chiral Molecules ◽  
Stereogenic Centers

scholarly journals Photoredox radical conjugate addition of dithiane-2-carboxylate promoted by an iridium(iii) phenyl-tetrazole complex: a formal radical methylation of Michael acceptors

2017 ◽  
Vol 8 (2) ◽  
pp. 1613-1620 ◽  
Author(s):  
Andrea Gualandi ◽  
Elia Matteucci ◽  
Filippo Monti ◽  
Andrea Baschieri ◽  
Nicola Armaroli ◽  
...  
Keyword(s):  
Michael Reaction ◽  
Conjugate Addition ◽  
Michael Acceptors

An iridium(iii) phenyl-tetrazole complex is a versatile catalyst for a new photocatalytic Michael reaction.

Enantioselective Organocatalytic Construction of Carbocycles: The Nicolaou Synthesis of Biyouyanagin A

2011 ◽  
Author(s):  
Douglass Taber
Keyword(s):  
Methyl Ether ◽  
Conjugate Addition ◽  
Unsaturated Aldehyde ◽  
Enantiomerically Pure ◽  
Intramolecular Alkylation ◽  
Stereogenic Centers ◽  
Chinese Academy Of Sciences ◽  
Academy Of Sciences ◽  
Polycyclic System ◽  
Selective Addition

One of the more powerful routes to enantiomerically-pure carbocycles is the desymmetrization of a prochiral ring. Karl Anker Jørgensen of Aarhus University has found (J. Am. Chem. Soc. 2007, 129, 441) that many cyclic β-ketoesters, including the vinylogous carbonate 1, can be homologated with 2 to the corresponding alkyne 3, in high ee. Sanzhong Luo of the Chinese Academy of Sciences, Beijing, and Jin-Pei Cheng, of the Chinese Academy of Sciences and Nankai University, have shown (J. Org. Chem. 2007, 72, 9350) that the catalyst 6 mediated the selective addition of 4-substituted cyclohexanones such as 4 to the nitroalkene 5, establishing three new stereogenic centers. Organocatalysts, alone or complexed with activating metals, have also been used to effect enantioselective ring construction. E. J. Corey of Harvard University has established (J. Am. Chem. Soc. 2007, 129, 12686) that the proline-derived complex 10 will mediate the 2 + 2 addition of a cyclic enol ether with an acrylate to give the cyclobutane 11. Further elaboration led to the cyclohexenone 12. Armando Córdova of Stockholm University has described (Tetrahedron Lett. 2007, 48, 5835) a novel route to cyclopentanones such as 16, via tandem conjugate addition/intramolecular alkylation. Professor Jørgensen has reported (Angew. Chem. Int. Ed . 2007, 46 , 9202) the double addition of 18 to the unsaturated aldehyde 17 to give 20. Earlier last year, Yujiro Hayashi of the Tokyo University of Science had shown (Angew. Chem. Int. Ed. 2007, 46, 4922) that the double addition of the inexpensive 21 to 5 could, depending on conditions, be directed selectively to 22, 23, or 24. As illustrated by the conversion of 8 to 13, organocatalysis can be used to effect the enantioselective construction of polycarbocyclic products. The initial ring prepared in enantiomerically-pure form by organocatalysis can also set the chirality of a polycyclic system. Professor Corey has reported (J. Am. Chem. Soc. 2007, 129, 10346) that Itsuno-Corey reduction of the prochiral diketone 25 led to the ketone 27. Cyclization followed by oxidation and reduction then delivered estrone methyl ether 28.

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