TY - JOUR
T1 - Synthesis of 2-nickela(II)oxetanes from nickel(0) and epoxides
T2 - Structure, reactivity, and a new mechanism of formation
AU - Desnoyer, Addison N.
AU - Bowes, Eric G.
AU - Patrick, Brian O.
AU - Love, Jennifer A.
PY - 2015/10/14
Y1 - 2015/10/14
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.5b06735
DO - 10.1021/jacs.5b06735
M3 - Article
AN - SCOPUS:84944345076
SN - 0002-7863
VL - 137
SP - 12748
EP - 12751
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 40
ER -