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

Schmid, Thibault E.; Drissi-Amraoui, Sammy; Crévisy, Christophe; Baslé, Olivier; Mauduit, Marc

doi:10.3762/bjoc.11.263

Cited by 51 publications

(17 citation statements)

References 42 publications

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“…Controlling the regioselectivity of copper‐catalyzed ACA reactions on extended conjugated systems while maintaining high enantioselectivities is a highly challenging issue, which proved to be dependent upon the nature of the electrophile and nucleophile as well as the catalytic system . In the initial screen, the ACA of Me 2 Zn to dienic acylimidazole substrate 1i occurred with very high 1,4‐selectivity.…”

Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope, Limitations and Iterative Reactions

et al. 2016

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An efficient copper-catalyzede nantioselective conjugate addition of dimethylzinc to unsaturated 2-acyl-N-methylimidazoles has been achieved using ac hiral bidentateh ydroxyalkyl-NHC ligand. Ther eactions proceed with excellent regioselectivity (1,4 vs. 1,6 and 1,8) in extended conjugateds ystems to affordt he 1,4-adducts in high enantioselectivities. This regioselectivity could be ascertained by DFT studies highlightingt he crucial role of the imidazole ring. Thanks to the development of efficient protocols to regenerate the unsaturated 2-acyl-N-methylimidazole moiety,a ni terative process has been developed ultimately leading to 3,5,7 all-syn or anti-anti polydeoxypropionate stereodiads.Scheme 5. Applicationo ft he ACA/post-functionalizations equence involving a,b-unsaturated 2-acyl-N-methylimidazole 1h to the synthesis of (+ +)-(S)-Florhydral .Scheme 6. Synthesis of unsaturated di-andt rienic2 -acyl-Nmethylimidazole subtrates 1i-n. Scheme 7. Substrate scope for the 1,4-regioselective ACAo f dimethylzinc to poly-unsaturated 2-acyl-N-methylimidazoles 1i-n catalyzed by L1/Cu(OTf) 2 .Scheme 12. Synthesis of anti,anti 3-(S),5-(R),7-(S)a cyl-N-methylimidazole 2p.

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Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope, Limitations and Iterative Reactions

et al. 2016

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“…In that respect, since the pioneering example reported by Alexakis and co-workers in 1993 [5], a wide range of cyclic and acyclic electron-deficient alkenes, such as α,β-unsaturated ketones, esters, nitriles, sulfones, or nitroolefines, was intensively studied, leading to the expected 1,4-products in excellent yields and remarkable enantioselectivities. More recently, tremendous breakthroughs were achieved in this field, notably by the formation of all-carbon quaternary chiral centers [6] and the challenging 1,6-, 1,8-, or 1,10-selective addition to cyclic or aliphatic polyenic substrates [7][8][9]. Furthermore, Cu ECA transformations were also successfully applied to the synthesis of natural products [10].…”

Section: Introductionmentioning

confidence: 99%

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

Pichon¹,

Morvan²,

Crévisy³

et al. 2020

Beilstein J. Org. Chem.

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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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“…However, 1,6-ACA has been described with a range of electrophiles, nucleophiles, metal-based catalysts, and chiral ligands families. [3][4][5][6][7][8][9] Mauduit et al have developed an efficient chiral tridentate P,N,O ligand, named diphenylphosphinoazomethinylate salt (DiPPAM, L), [10] which has proved its efficiency for copper-catalyzed 1,6-ACA of dialkylzinc reagents to cyclic [5,7] and more recently to acyclic [11][12][13] dienones (Scheme 1). While good to excellent regioselectivity and enantioselectivity could be achieved with this catalytic system, attempts to characterize intermediates were unsuccessful and the active catalytic species has remained unidentified.…”

Section: Introductionmentioning

confidence: 99%

Catalytically Active Species in Copper/DiPPAM‐Catalyzed 1,6‐Asymmetric Conjugate Addition of Dialkylzinc to Dienones: A Computational Overview

et al. 2019

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Four different catalytically active species are computationally examined in order to investigate the mechanism of Cu/DiPPAM‐catalyzed 1,6‐conjugate addition of dialkylzinc to acyclic dienones. A DiPPAM‐bridged Cu(alkyl)‐Zn(acetate) bimetallic complex exhibits the best catalytic activity, which can be associated with the best balance between the stability of the dienone adduct and its activation by copper. The selectivities (regio‐ and enantioselectivity) associated with the retained mechanism are investigated by DFT calculations and successfully compared to experimental data, including the critical influence of the substituents within the dienone on the regioselectivity and the obtained enantioselectivity for the formation of one 1,6‐adduct.

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

Cited by 51 publications

References 42 publications

Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope, Limitations and Iterative Reactions

Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope, Limitations and Iterative Reactions

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

Catalytically Active Species in Copper/DiPPAM‐Catalyzed 1,6‐Asymmetric Conjugate Addition of Dialkylzinc to Dienones: A Computational Overview

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