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

Kyohei Kanomata, Yasunori Toda, Yukihiro Shibata, Masahiro Yamanaka, Seiji Tsuzuki, Ilya D. Gridnev, Masahiro Terada

Research output: Contribution to journalArticlepeer-review

44 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)3515-3523
Number of pages9
JournalChemical Science
Volume5
Issue number9
DOIs
Publication statusPublished - 2014 Sep

ASJC Scopus subject areas

  • Chemistry(all)

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