title: Enantioselective catalytic alpha-alkylation of aldehydes via an SN1 pathway.
abstract: 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.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Adam R
authors.initials: AR
authors.lastname: Brown
authors.forename: Wen-Hsin
authors.initials: WH
authors.lastname: Kuo
authors.forename: Eric N
authors.initials: EN
authors.lastname: Jacobsen
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000478:Alkylation; D002384:Catalysis; D006842:Hydrocarbons, Brominated; D055601:Organic Chemistry Phenomena; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D006842:Hydrocarbons, Brominated; C005218:methyl bromide