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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
Author(s) -
Galván Alicia,
GonzálezPérez Adán B.,
Álvarez Rosana,
de Lera Angel R.,
Fañanás Francisco J.,
Rodríguez Félix
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201511231
Subject(s) - steric effects , catalysis , enantioselective synthesis , chemistry , denticity , brønsted–lowry acid–base theory , context (archaeology) , computational chemistry , stereochemistry , transition state , combinatorial chemistry , organic chemistry , crystal structure , paleontology , biology
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.