Chelation-controlled addition of organozincs to α-chloro aldimines

J Am Chem Soc. 2012 Oct 24;134(42):17599-604. doi: 10.1021/ja306781z. Epub 2012 Oct 10.

Abstract

Nucleophilic additions to α-chiral α-halo carbonyl derivatives are well-known to generate Cornforth-Evans products via a nonchelation pathway. What was unprecedented before this report is C-X bonds reversing the diastereoselectivity through coordination to metals during C-C bond-forming reactions (chelation control). Herein we describe chelation control involving C-X bonds in highly diastereoselective additions of organozinc reagents to a variety of α-chloro aldimines. The unique ability of alkylzinc halide Lewis acids to coordinate to the Cl, N, and O of α-chloro sulfonyl imine substrates is supported by computational studies.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Amines / chemical synthesis*
  • Amines / chemistry
  • Chelating Agents / chemistry*
  • Imines / chemistry*
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Stereoisomerism
  • Zinc / chemistry*

Substances

  • Amines
  • Chelating Agents
  • Imines
  • Organometallic Compounds
  • Zinc