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Synthesis of 2-Nickela(II)oxetanes from Nickel(0) and Epoxides: Structure, Reactivity, and a New Mechanism of Formation

TitleSynthesis of 2-Nickela(II)oxetanes from Nickel(0) and Epoxides: Structure, Reactivity, and a New Mechanism of Formation
Publication TypeJournal Article
Year of Publication2015
AuthorsDesnoyer, AN, Bowes, EG, Patrick, BO, Love, JA
JournalJournal of the American Chemical Society
Volume137
Pagination12748-12751
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.

URLhttp://dx.doi.org/10.1021/jacs.5b06735
DOI10.1021/jacs.5b06735