title: Mechanistic study of nickel-catalyzed ynal reductive cyclizations through kinetic analysis.
abstract: The mechanism of nickel-catalyzed, silane-mediated reductive cyclization of ynals has been evaluated. The cyclizations are first-order in [Ni] and [ynal] and zeroth-order in [silane]. These results, in combination with the lack of rapid silane consumption upon reaction initiation, are inconsistent with mechanisms involving reaction initiation by oxidative addition of Ni(0) to the silane. Silane consumption occurs only when both the alkyne and aldehyde are present. Mechanisms involving rate-determining oxidative cyclization to a metallacycle followed by rapid reaction with the silane are consistent with the data obtained.
authors: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, United States.
authors: Ryan D
authors: RD
authors: Baxter
authors: John
authors: J
authors: Montgomery
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D003500:Cyclization; D007700:Kinetics; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D012821:Silanes / Q000737:chemistry*
chemical_list: D000475:Alkenes; D012821:Silanes; D009532:Nickel