Carbonyl Olefin Metathesis and Dehydrogenative Cyclization of Aromatic Ketones and gem-Difluoroalkenes

The beauty of one-pot cascade reaction lies in the efficient disconnection and construction of several bonds in a single reaction flask, without the isolation of any intermediates. Herein, we report the first photoinduced thermally promoted cascade reactions of readily available aromatic ketones and aromatic gem-difluoroalkenes for the synthesis of phenanthrenes which possess potential utility in drug design and materials science. The reaction combines carbonyl-olefin metathesis (cascade photoinduced [2+2] cyclization and thermally controlled retro [2+2] cyclization) and dehydrogenative cyclization (cascade photoinduced conrotatory 6 pi electrocyclization and collidine-promoted dehydrogenative aromatization) together in one pot. The oxidant-free, acid-free and metal-free reaction shows broad substrate scope and wide functional group tolerance.