Issue 9, 2014

Secondary stereocontrolling interactions in chiral Brønsted acid catalysis: study of a Petasis–Ferrier-type rearrangement catalyzed by chiral phosphoric acids

Abstract

Chiral phosphoric acids have emerged as promising asymmetric Brønsted acid catalysts that harness hydrogen bonding interactions as key stereocontrolling elements. A new approach to chiral phosphoric acid catalysis through ion-pairing interactions between the anionic conjugate base of the catalyst and a cationic electrophile has recently attracted attention. However, the mechanism of stereocontrol through ion-pairing interactions is still elusive. As a probe reaction for studying the stereocontrolling element involved in such catalytic reactions, we investigated the Petasis–Ferrier-type rearrangement of a 7-membered cyclic vinyl acetal catalyzed by chiral phosphoric acids. DFT calculations suggested that non-classical C–H⋯O hydrogen bonds between the catalyst and the substrate play an important role in determining the stereoselectivity. In addition, π–π stacking interactions were found to be a key factor for stereocontrol when using a 9-anthryl group-bearing catalyst.

Graphical abstract: Secondary stereocontrolling interactions in chiral Brønsted acid catalysis: study of a Petasis–Ferrier-type rearrangement catalyzed by chiral phosphoric acids

Supplementary files

Article information

Article type
Edge Article
Submitted
26 Feb 2014
Accepted
09 May 2014
First published
09 May 2014

Chem. Sci., 2014,5, 3515-3523

Author version available

Secondary stereocontrolling interactions in chiral Brønsted acid catalysis: study of a Petasis–Ferrier-type rearrangement catalyzed by chiral phosphoric acids

K. Kanomata, Y. Toda, Y. Shibata, M. Yamanaka, S. Tsuzuki, I. D. Gridnev and M. Terada, Chem. Sci., 2014, 5, 3515 DOI: 10.1039/C4SC00611A

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