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Issue 9, 2014
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Secondary stereocontrolling interactions in chiral Brønsted acid catalysis: study of a Petasis–Ferrier-type rearrangement catalyzed by chiral phosphoric acids

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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

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Supplementary files

Article information


Submitted
26 Feb 2014
Accepted
09 May 2014
First published
09 May 2014

Chem. Sci., 2014,5, 3515-3523
Article type
Edge Article
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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