Diastereo- and Enantioselective Construction of Vicinal Stereocenters through Tandem Electrochemical Dearomatization and Allylic Alkylation

The dearomatization of arenes represents a powerful synthetic strategy for constructing three-dimensional cyclic architectures. However, due to their inherently high aromatization energy, the enantioselective dearomatization of nonactivated all-carbon arenes remains a challenge. On the other hand, the vicinal stereocenter is widely present in natural products and bioactive molecules, and its construction is an important research topic in organic synthesis. In this paper, we report a strategy for the enantioselective construction of vicinal stereocenters, which combines an electrochemical dearomatization of arenes and a silver-catalyzed allylic alkylation. Using this method, starting from naphthylsilanes, a broad range of chiral homoallylic alcohols containing a 1,4-dihydronaphthalene moiety were synthesized with high regio-, diastereo- and enantioselectivities.