Exploiting the Multidentate Nature of Chiral Disulfonimides in a Multicomponent Reaction for the Asymmetric Synthesis of Pyrrolo[1,2-a]indoles: A Remarkable Case of Enantioinversion

Angewandte Chemie
Alicia GalvánFélix Rodríguez

Abstract

A new multicomponent coupling reaction for the enantioselective synthesis of pyrrolo[1,2-a]indoles under the catalysis of a chiral disulfonimide is described. The high specificity of the reaction is a consequence of the multidentate character of the Brønsted acid catalyst. Insights from DFT calculations helped explain the unexpected high enantioselectivity observed with the simplest 3,3'-unsubstituted binaphthyl catalyst as a result of transition-state stabilization by a network of cooperative noncovalent interactions. The remarkable enantioinversion resulting from the simple introduction of substituents at 3- and 3'-positions, the first reported example of this phenomenon in the context of binaphthalene-derived Brønsted acid catalysis, was instead attributed to destabilizing steric interactions.

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Citations

Jul 28, 2016·Journal of the American Chemical Society·Sayantani DasBenjamin List
Sep 10, 2016·Organic Letters·Fengtao Zhou, Hisashi Yamamoto
Sep 18, 2020·Organic & Biomolecular Chemistry·Meghan C Benda, Stefan France

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