Development of a\nHighly Enantioselective Catalytic\nDi-π-methane Rearrangement

The di-π-methane (DPM) rearrangement\nis an important\norganic\nphotorearrangement that converts 1,4-diene-containing compounds to\nvinyl cyclopropanes, often resulting in extensive, synthetically valuable\nrestructuring of the substrate’s carbon framework. We investigated\nthe influence of Lewis and Brønsted acids on the DPM rearrangement\nof dibenzobarrelenes. These studies have culminated in the identification\nof a dual chiral Brønsted acid–iridium photosensitizer\nsystem that enables the first highly enantioselective catalytic all-carbon\nDPM rearrangement.