Alcohols are the most common functional group present in small molecule drugs and hydroxyls are often used as chemical handles for further syntheses. Despite obvious limitations, Grignard reactions remains among the most-used reactions for C-C bond formation using carbonyls. Current catalytic methods for the synthesis of benzylic alcohols often require preparation of highly reactive organometallic reagents and are limited to reactions with aromatic aldehydes and ketones. We report here that nickel complexes catalyze the addition of aryl halides to aromatic and aliphatic aldehydes in the presence of zinc metal as a reducing agent. Acidic functional groups and sterically hindered substrates are well tolerated and couple in high yield, expanding the pool of synthetically available alcohols. Preliminary mechanistic investigations show the key bond-forming step is a 1,2-migratory insertion of an arylnickel intermediate across the carbonyl in the presence of a Lewis acid co-catalyst (ZnBr<sub>2</sub>).

Nickel-catalyzed arylation of aldehydes to form secondary alcohols

2019 Fall National Meeting

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