title: Rationalization of an unusual solvent-induced inversion of enantiomeric excess in organocatalytic selenylation of aldehydes.
abstract: 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 C-Se 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.
authors.affiliation: Department of Chemistry, Scripps Research Institute, 10550 N. Torrey Pines Rd., La Jolla, CA 92037 (USA); Imperial College of Science, Medicine and Technology, Department of Chemistry, London SW7 2AZ (UK).
authors.forename: Jordi
authors.initials: J
authors.lastname: Burés
authors.forename: Paul
authors.initials: P
authors.lastname: Dingwall
authors.forename: Alan
authors.initials: A
authors.lastname: Armstrong
authors.forename: Donna G
authors.initials: DG
authors.lastname: Blackmond
keywords: enantioselectivity; kinetics; organocatalysis; reaction mechanisms; solvent effects