Synthesis of vinyl-substituted alcohols using acetylene as a C2 building block.

ABSTRACT

Vinyl-substituted alcohols represent a highly useful class of molecular skeletons. The current method typically requires either stoichiometric metallic reagents or preformed precursors. Herein, we report a nickel catalysis-enabled synthesis of vinyl-substituted alcohols via a 5-membered oxa-metallacycle. In this protocol, acetylene, the simplest alkyne and abundant feedstock, is employed as an ideal C2 synthon. The reaction features mild conditions, good functional group tolerance and broad substrate scope. Mechanistic exploration implies that the oxa-metallacycle originated from the cyclometallation of aldehyde and acetylene is the key intermediate for this transformation, which is then terminated by a silane-mediated σ-bond metathesis and subsequent reductive elimination.