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

Asymmetric ring opening (ARO) of strained oxa-and azabicyclic al-kenes has emerged as a powerful tool for the construction of chiral cyclic molecules with multiple stereocenters. In this article, we suc-cessfully apply the strategy of cross-electrophile coupling in the ARO reaction of oxa-and azabicyclic alkenes. While previous re-ports 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-open-ing reaction offers an efficient entry to highly enantioenriched 1,2-dihydronaphthalenes with full cis -selectivity.

Automated summary

Asymmetric ring opening (ARO) is a powerful tool for constructing chiral cyclic molecules with multiple stereocenters. In this article, the strategy of cross-electrophile coupling is successfully applied to the ARO reaction of oxa- and azabicyclic alkenes. By using functionalized alkyl bromides as coupling partners, highly enantioenriched 1,2-dihydronaphthalenes with full cis-selectivity can be efficiently synthesized under the catalysis of a chiral nickel complex.