Atom-Economical Ni-Catalyzed Diborylative Cyclization of Enynes: Preparation of Unsymmetrical Diboronates

We report a Ni-catalyzed diborylative cyclization of enynes that affords carbo- and heterocycles containing both alkyl- and alkenylboronates. The reaction is fully atom-economical, shows a broad scope, and employs a powerful and inexpensive catalytic Ni-based system. The reaction mechanism seems to involve activation of the enyne by Ni(0) through oxidative cyclometalation of the enyne prior to diboron reagent activation. An unprecedented dinuclear bis­(organometallic) Ni­(I) intermediate complex was isolated.