Issue 8, 2015

Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

Abstract

We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C–H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.

Graphical abstract: Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Apr 2015
Accepted
29 May 2015
First published
12 Jun 2015
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., 2015,6, 4479-4483

Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

J. Park, K. G. M. Kou, D. K. Kim and V. M. Dong, Chem. Sci., 2015, 6, 4479 DOI: 10.1039/C5SC01553G

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.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements