Enantioselective catalytic alpha-alkylation of aldehydes via an SN1 pathway.
Primary aminothiourea derivatives are shown to catalyze enantioselective alkylation of alpha-arylpriopionaldehdyes with diarylbromomethane. Evidence for a stepwise, S(N)1 mechanism in the substitution reaction induced by anion binding to the catalyst is provided by catalyst structure-activity studies, kinetic isotope effects, linear free-energy relationship studies, and competition experiments.
Brown
Adam R
AR
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Kuo
Wen-Hsin
WH
Jacobsen
Eric N
EN
D000447:Aldehydes / Q000737:chemistry*; D000478:Alkylation; D002384:Catalysis; D006842:Hydrocarbons, Brominated; D055601:Organic Chemistry Phenomena; D013237:Stereoisomerism
D000447:Aldehydes; D006842:Hydrocarbons, Brominated; C005218:methyl bromide