title: Mechanistic investigation of the enantioselective intramolecular stetter reaction: proton transfer is the first irreversible step.
abstract: A study on the mechanism of the asymmetric intramolecular Stetter reaction is reported. This investigation includes the determination of the rate law, kinetic isotope effects, and competition experiments. The reaction was found to be first order in aldehyde and azolium catalyst or free carbene. A primary kinetic isotope effect was found for the proton of the aldehyde. Taken together with a series of competition experiments, these results suggest that proton transfer from the tetrahedral intermediate formed upon nucleophilic attack of the carbene onto the aldehyde is the first irreversible step.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States.
authors.forename: Jennifer L
authors.initials: JL
authors.lastname: Moore
authors.forename: Anthony P
authors.initials: AP
authors.lastname: Silvestri
authors.forename: Javier Read
authors.initials: JR
authors.lastname: de Alaniz
authors.forename: Daniel A
authors.initials: DA
authors.lastname: DiRocco
authors.forename: Tomislav
authors.initials: T
authors.lastname: Rovis
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D011522:Protons; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D011522:Protons