Oxa- and Azabenzonorbornadienes as Electrophilic Partners under Photoredox/Nickel Dual Catalysis

Herein, the introduction of oxa- and azabenzonorbornadienes into photoredox/nickel dual catalysis in a regioselective and diastereoselective transformation is disclosed. The inherent advantages of this dual catalytic system allow the use of alkyl motifs forming exclusively cis-1,2-dihydro-1-naphthyl alcohol backbones using readily accessible 4-alkyl-1,4-dihydropyridines (DHPs). Whereas previous studies have emphasized the use of nucleophilic organometallic coupling partners, this protocol grants access to a rather unexplored core featuring alkyl residues, while avoiding the use of highly reactive organometallic species (i.e., M = Al, Mg, Li, Zn, Zr). Density functional theory (DFT) calculations support an oxidative addition/reductive elimination mechanism, followed by a Curtin–Hammett scenario that controls the regioselectivity of the process, unlike previously reported transformations that proceed via a carbometalation/β-oxygen elimination mechanism.