Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones.

Chemical Science
Lin ZhangDarren J Dixon

Abstract

The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles via an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(i) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.

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Citations

Mar 31, 2021·Angewandte Chemie·Zhao YangMin Zhang

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Methods Mentioned

BETA
X-ray

Software Mentioned

COSMO
Amsterdam Density Functional ( ADF )

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