Synthesis of 7-Arylthiomethyl Dibenzo[ b , d ]azepines through Imidoylative Heck Cyclization and CPA-Catalyzed Thio-Michael Addition/Enantioselective Protonation.

A chiral phosphoric acid-catalyzed thio-Michael addition/enantioselective protonation has been developed for the first time. The reaction applies 7-methylene-6-aryl-7 H -dibenzo[ b,d ]azepines, products of Pd-catalyzed imidoylative Heck cyclization, as Michael acceptors in reactions with a wide range of aryl thiols. Diversified 7-[(arylthio)methyl]-7 H -dibenzo[ b,d ]azepines bearing a benzylic stereocenter and a thermodynamically regulated biaryl axis were produced with good to excellent enantioselectivity and 14-25:1 diastereoisomeric ratios.