title: Catalytic asymmetric γ-alkylation of carbonyl compounds via stereoconvergent Suzuki cross-couplings.
abstract: With the aid of a chiral nickel catalyst, enantioselective γ- (and δ-) alkylations of carbonyl compounds can be achieved through the coupling of γ-haloamides with alkylboranes. In addition to primary alkyl nucleophiles, for the first time for an asymmetric cross-coupling of an unactivated alkyl electrophile, an arylmetal, a boronate ester, and a secondary (cyclopropyl) alkylmetal compound are shown to couple with significant enantioselectivity. A mechanistic study indicates that cleavage of the carbon-halogen bond of the electrophile is irreversible under the conditions for asymmetric carbon-carbon bond formation.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
authors.forename: Susan L
authors.initials: SL
authors.lastname: Zultanski
authors.forename: Gregory C
authors.initials: GC
authors.lastname: Fu
mesh_terms: D000478:Alkylation; D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D007659:Ketones; D009942:Organometallic Compounds; D009532:Nickel