Catalytic enantioselective allene–anhydride approach to β,γ-unsaturated enones bearing an α-all-carbon-quarternary center

Yuan Yuan; Xue Zhang; Hui Qian; Shengming Ma

doi:10.1039/D0SC03227A

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Catalytic enantioselective allene–anhydride approach to β,γ-unsaturated enones bearing an α-all-carbon-quarternary center†

Yuan Yuan,^a Xue Zhang,

*^b Hui Qian

*^a and Shengming Ma

*^ab

Author affiliations

* Corresponding authors

^a Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai 200433, P. R. China
E-mail: qian_hui@fudan.edu.cn

^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu,, Shanghai 200032, P. R. China
E-mail: masm@sioc.ac.cn

Abstract

A protocol of highly regio- and enantioselective copper-catalyzed hydroacylation of the non-terminal C [double bond, length as m-dash] C bond in 1,1-disubstituted terminal allenes with anhydrides has been developed. Both aromatic and aliphatic carboxylic anhydrides are applicable to the efficient construction of all carbon quarternary centers connected with a versatile CC bond and a useful ketone functionality. The synthetic potentials of the enantioenriched products have also been demonstrated. Density functional theory (DFT) calculations were performed to explain the steric outcome of the products: the hydroacylation proceeds through a six-membered transition state and the ligand-substrate steric interactions account for the observed enantioselectivity although the chiral ligand is far away from the to-be-genetated chiral center.

This article is part of the themed collection: 2020 Chemical Science HOT Article Collection

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DOI: https://doi.org/10.1039/D0SC03227A
Article type: Edge Article
Submitted: 10 Jun 2020
Accepted: 22 Jul 2020
First published: 22 Jul 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2020,11, 9115-9121

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Catalytic enantioselective allene–anhydride approach to β,γ-unsaturated enones bearing an α-all-carbon-quarternary center

Y. Yuan, X. Zhang, H. Qian and S. Ma, Chem. Sci., 2020, 11, 9115 DOI: 10.1039/D0SC03227A

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Chemical Science

Catalytic enantioselective allene–anhydride approach to β,γ-unsaturated enones bearing an α-all-carbon-quarternary center†

Abstract

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Catalytic enantioselective allene–anhydride approach to β,γ-unsaturated enones bearing an α-all-carbon-quarternary center

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