title: Synthesis of 2-Nickela(II)oxetanes from Nickel(0) and Epoxides: Structure, Reactivity, and a New Mechanism of Formation.
abstract: 2-Nickelaoxetanes have been frequently invoked as reactive intermediates in catalytic reactions of epoxides using nickel, but have never been isolated or experimentally observed in these transformations. Herein, we report the preparation of a series of well-defined nickelaoxetanes formed via the oxidative addition of nickel(0) with epoxides featuring ketones. The stereochemistry of the products is retained, which has not yet been reported for nickelaoxetanes. Theoretical calculations support a bimetallic ring-opening/closing pathway over a concerted oxidative addition. Initial reactivity studies of a nickelaoxetane demonstrated protonolysis, oxidatively induced reductive elimination, deoxygenation, and elimination reactions when treated with the appropriate reagents.
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Addison N
authors.initials: AN
authors.lastname: Desnoyer
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Eric G
authors.initials: EG
authors.lastname: Bowes
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Brian O
authors.initials: BO
authors.lastname: Patrick
authors.affiliation: Department of Chemistry, The University of British Columbia , Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Jennifer A
authors.initials: JA
authors.lastname: Love