Issue 28, 2020

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.

Graphical abstract: Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones

Supplementary files

Article information

Article type
Edge Article
Submitted
21 May 2020
Accepted
23 Jun 2020
First published
24 Jun 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 7444-7450

Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones

L. Zhang, K. Yamazaki, J. A. Leitch, R. Manzano, V. A. M. Atkinson, T. A. Hamlin and D. J. Dixon, Chem. Sci., 2020, 11, 7444 DOI: 10.1039/D0SC02878A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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