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DOI: 10.1055/s-0036-1591548
Copper-Catalyzed Enantioselective Coupling between Allylboronates and Phosphates Using a Phenol–Carbene Chiral Ligand: Asymmetric Synthesis of Chiral Branched 1,5-Dienes
This work was supported by Grants-in-Aid for Scientific Research (B) (No. 15H03803), JSPS to H.O. and by CREST and ACT-C, JST to M.S.Publication History
Received: 19 December 2017
Accepted after revision: 12 February 2018
Publication Date:
20 March 2018 (online)
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Abstract
Details of the Cu-catalyzed enantioselective allyl–allyl coupling reaction between allylboronates and (Z)-allylic phosphates using a new chiral N-heterocyclic carbene (NHC) ligand containing a phenolic hydroxy group are presented. The copper catalysis delivers enantioenriched chiral 1,5-dienes with a tertiary stereogenic center. Compatibility with various functional groups and the use of earth-abundant and relatively low-toxicity copper as a metal are attractive features of this protocol. The utility of the chiral phenol–NHC ligand for enantioselective copper catalysis with organoboron compounds is demonstrated and enantiodiscrimination models are discussed.
Key words
asymmetric catalysis - allylic substitution - synthetic methods copper catalysis - organoboron compoundsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591548.
- Supporting Information
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See also:
For selected papers, see:
For reviews on Cu-catalyzed allylic substitutions, see:
For Cu-catalyzed enantioselective allylic substitutions using organoboron reagents and oxygen-functionalized NHC chiral ligands, see:
See also:
For our previous work, see:
For functionalized NHC ligands in asymmetric catalysis, see:
See also:
Nakamura and co-workers conducted DFT calculations on the mechanism of the reaction between [MeCu(CN)Li] and allyl acetate to form a square planar, four-coordinate (γ-σ-enyl)copper(III) species [(π-en-σ-yl)copper(III) complex]. Our mechanistic proposal is in accord with Nakamura’s mechanism, in which the (γ-σ-enyl)copper(III) species is not in equilibrium with the corresponding (α-σ-enyl)copper(III) species; the regioselectivity is determined at the oxidative addition step as a consequence of the asymmetric nature of MeCuCN–. Our proposed mechanism is in accord with Nakamura’s mechanism in that the reaction proceeds through oxidative addition of a cuprate to form the (γ-σ-enyl)copper(III) species followed by reductive elimination. However, the coordination number of copper in the allylcopper(III) complex is different by virtue of bidentate coordination of the anionic phenol–NHC chiral ligand (L). The strongly electron-donating NHC coordination should render the π-en coordination weaker, making the allylic 1,3-copper migration in the allylcopper(III) complex more feasible. See:
For the effect of a σ-donor ligand, see: