Identifying the Imperative Role of Metal-Olefin Interactions in Catalytic C-O Reductive Elimination from Nickel(II).

ABSTRACT: We present a series of experimental and computational mechanistic investigations of an unusually facile example of Ni-catalyzed C-O bond formation. Our method, originally reported in 2016, involves the formation of cyclic enol ethers from vinyl iodides bearing pendant alcohol groups. Our findings suggest that the observed reactivity arises from the coordination of the olefin in the vinyl iodide starting material and the enol ether product with Ni(0) intermediates. Density functional theory calculations reveal a plausible catalytic mechanism involving a Ni(II)/Ni(0) redox cycle featuring two-electron C-I oxidative addition and C-O reductive elimination steps. The direct formation of a η ²-enol ether Ni(0) complex from a key Ni(II) alkoxide intermediate dramatically alters

SUBMITTER: Lohrey TD 

PROVIDER: S-EPMC8849544 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature