Organic Chemistry

Dual Catalytic Enantioselective Desymmetrization of Allene-Tethered Cyclohexanones

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.

Content

Thumbnail image of Chem Rxiv Manuscript.pdf

Supplementary material

Thumbnail image of Copper Allene Supporting Information.pdf
Copper Allene Supporting Information
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TOC
Thumbnail image of crystallographic data.txt
crystallographic data