Nickel-catalyzed reductive asymmetric alkylative ring opening of oxa- and azabicyclic alkenes

Asymmetric ring opening (ARO) of strained oxa- and azabicyclic alkenes has emerged as a powerful tool for the construction of chiral cyclic molecules with multiple stereocenters. In this article, we successfully apply the strategy of cross-electrophile coupling in the ARO reaction of oxa- and azabicyclic alkenes. While previous reports have focused on the use of nucleophilic organometallics, this work enables the direct use of functionalized alkyl bromides as the coupling partners with 7-oxa and azabenzonorbornadienes. Under the catalysis of a chiral nickel complex, this desymmetric-ring-opening reaction offers an efficient entry to highly enantioenriched 1,2-dihydronaphthalenes with full cis-selectivity.