Premium
Rationalization of an Unusual Solvent‐Induced Inversion of Enantiomeric Excess in Organocatalytic Selenylation of Aldehydes
Author(s) -
Burés Jordi,
Dingwall Paul,
Armstrong Alan,
Blackmond Donna G.
Publication year - 2014
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.201404327
Subject(s) - enamine , organocatalysis , chemistry , enantiomer , catalysis , solvent , enantioselective synthesis , selectivity , rationalization (economics) , silyl ether , organic chemistry , stereochemistry , silylation , philosophy , epistemology
An unusual solvent‐induced inversion of the sense of enantioselectivity observed in the α‐selenylation of aldehydes catalyzed by a diphenylprolinol silyl ether catalyst is correlated to the presence of intermediates formed subsequent to the highly selective CSe bond‐forming step in the catalytic cycle. This work provides support for a mechanistic concept for enamine catalysis and includes a general role for “downstream intermediates” in selectivity outcomes in organocatalysis.