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. 2021 Dec 10;6(50):35093-35103.
doi: 10.1021/acsomega.1c05875. eCollection 2021 Dec 21.

Crown Ether-Derived Chiral BINOL: Enantioselective Michael Addition of Alkenyl Boronic Acids to α,β-Unsaturated Ketones

Jia-Ju Tao  1 , Jia-Dong Tang  1 , Tao Hong  1 , Jia-Wen Ye  1 , Jia-Yu Chen  1 , Chunsong Xie  1 , Zibin Zhang  1 , Shijun Li  1
Affiliations

Crown Ether-Derived Chiral BINOL: Enantioselective Michael Addition of Alkenyl Boronic Acids to α,β-Unsaturated Ketones

Jia-Ju Tao et al. ACS Omega. .

Abstract

A new class of aza-crown ether-derived chiral BINOL catalysts were designed, synthesized, and applied in the asymmetric Michael addition of alkenylboronic acids to α,β-unsaturated ketones. It was found that introducing aza-crown ethers to the BINOL catalyst could achieve apparently higher enantioselectivity than a similar BINOL catalyst without aza-crown ethers did, although the host-guest complexation of alkali ions by the aza-crown ethers could not further improve the catalysis effectiveness. Under mediation of the aza-crown ether-derived chiral BINOL and in the presence of a magnesium salt, an array of chiral γ,δ-unsaturated ketones were furnished in good enantioselectivities (81-95% ees).

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis of the Crown Ether-Derived BINOL Catalysts (S)-1
Scheme 2
Scheme 2. Substrate Scope of α,β-Unsaturated Ketones and Styrylboronic Acids
Reaction conditions: 0.04 mmol α,β-unsaturated carbonyl substrate, substrate concentration = 0.05 M. bIsolated yield. cDetermined by HPLC analysis.
Figure 1
Figure 1
Proposed Catalytic Mechanism.
See this image and copyright information in PMC

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