Synfacts 2013; 9(1): 0073
DOI: 10.1055/s-0032-1317780
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Negishi Reaction of Racemic Benzylic Bromides and Alkylzinc Reagents

Contributor(s):
Hisashi Yamamoto
,
Jiajing Tan
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
Further Information

Publication History

Publication Date:
17 December 2012 (online)

 

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.


#
#