title: Chelation-controlled addition of organozincs to α-chloro aldimines.
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.
authors.affiliation: Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Gretchen R
authors.initials: GR
authors.lastname: Stanton
authors.forename: Per-Ola
authors.initials: PO
authors.lastname: Norrby
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Walsh
mesh_terms: D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D002614:Chelating Agents / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry*
chemical_list: D000588:Amines; D002614:Chelating Agents; D007097:Imines; D009942:Organometallic Compounds; D015032:Zinc