We disclose a Ni-catalyzed vicinal
difunctionalization of alkenes
with benzyl halides and alkylzinc reagents, which produces products
with two new alkyl–alkyl bonds. This alkene dialkylation is
effective in combining secondary benzyl halides and secondary alkylzinc
reagents with internal alkenes, which furnishes products with three
contiguous all-carbon secondary stereocenters. The products can be
readily elaborated to access complex tetralene, benzosuberene, and
bicyclodecene cores. The reaction also features as the most efficient
alkene difunctionalization process to date with catalyst loadings
down to 500 ppm and the catalytic turnover number (TON) and turnover
frequency (TOF) registering up to 2 × 103 and 165
h–1 at rt, respectively.