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

Chiral phosphoric acids have emerged as promising asymmetric Broensted 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 a...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2014-07, Vol.5 (9), p.3515-3523
Main Authors: Kanomata, Kyohei, Toda, Yasunori, Shibata, Yukihiro, Yamanaka, Masahiro, Tsuzuki, Seiji, Gridnev, Ilya D, Terada, Masahiro
Format: Article
Language:English
Subjects:
Asymmetry
Catalysis
Catalysts
Chemical reactions
Conjugates
Hydrogen bonding
Mathematical analysis
Phosphoric acid
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Summary:Chiral phosphoric acids have emerged as promising asymmetric Broensted 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, pi - pi stacking interactions were found to be a key factor for stereocontrol when using a 9-anthryl group-bearing catalyst.
ISSN:2041-6520
2041-6539
DOI:10.1039/c4sc00611a