Binder JT, Cordier CJ, Fu GC * Massachusetts Institute of Technology, Cambridge and
California Institute of Technology, Pasadena, USA
Catalytic Enantioselective Cross-Couplings of Secondary Alkyl Electrophiles with Secondary
Alkylmetal Nucleophiles: Negishi Reactions of Racemic Benzylic Bromides with Achiral
Alkylzinc Reagents.
J. Am. Chem. Soc. 2012;
134: 17003-17006
Key words
nickel - Negishi coupling - oxazoline ligands
Significance
Reported here is an enantioselective cross-coupling of racemic benzylic bromides with
achiral alkylzinc reagents. A novel bidentate oxazoline-type ligand was developed,
leading to the desired products in good yield and enantioselectivity.
Comment
It is surprising that both reagents are achiral. For acyclic alkylzinc reagents, an
usual isomerization was observed and a substantial amount of a branched product was
generated from an unbranched nucleophile.
