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

Authors :
Masahiro Yamanaka
Masahiro Terada
Ilya D. Gridnev
Yukihiro Shibata
Kyohei Kanomata
Yasunori Toda
Seiji Tsuzuki
Source :
Chem. Sci.. 5:3515-3523
Publication Year :
2014
Publisher :
Royal Society of Chemistry (RSC), 2014.

Abstract

Chiral phosphoric acids have emerged as promising asymmetric Bronsted 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.

Details

ISSN :
20416539 and 20416520
Volume :
5
Database :
OpenAIRE
Journal :
Chem. Sci.
Accession number :
edsair.doi...........11558a2050874f90e18b46d846fb169d
Full Text :
https://doi.org/10.1039/c4sc00611a