title: Nickel-catalyzed enantioselective cross-couplings of racemic secondary electrophiles that bear an oxygen leaving group.
abstract: To date, effective nickel-catalyzed enantioselective cross-couplings of alkyl electrophiles that bear oxygen leaving groups have been limited to reactions of allylic alcohol derivatives with Grignard reagents. In this Communication, we establish that, in the presence of a nickel/pybox catalyst, a variety of racemic propargylic carbonates are suitable partners for asymmetric couplings with organozinc reagents. The method is compatible with an array of functional groups and utilizes commercially available catalyst components. The development of a versatile nickel-catalyzed enantioselective cross-coupling process for electrophiles that bear a leaving group other than a halide adds a significant new dimension to the scope of these reactions.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Oelke
authors.forename: Jianwei
authors.initials: J
authors.lastname: Sun
authors.forename: Gregory C
authors.initials: GC
authors.lastname: Fu
mesh_terms: D000480:Alkynes / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D002626:Chemistry, Pharmaceutical / Q000379:methods; D003432:Cross-Linking Reagents / Q000737:chemistry; D015195:Drug Design; D004563:Electrochemistry / Q000379:methods; D006801:Humans; D006967:Hypersensitivity / Q000188:drug therapy; D007249:Inflammation / Q000188:drug therapy; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000480:Alkynes; D003432:Cross-Linking Reagents; D002244:Carbon; D009532:Nickel; D010100:Oxygen