2018 Volume 76 Issue 11 Pages 1185-1196
Catalytic synthesis of heteroles via the cleavage of carbon-heteroatom bonds is described. The rhodium-catalyzed reaction of 2-silylphenylboronic acids with internal alkynes gives 2,3-disubstituted benzosilole derivatives with loss of a substituent in the triorganosilyl group of the staring material. π-Extended phospholes and thiophenes were found to be synthesized by the palladium-catalyzed reactions of normally unreactive tertiary phosphines and sulfides through the cleavage of carbon-phosphorus and carbon-sulfur bonds, respectively. In addition, double cleavage of carbon-phosphorus bonds of bisphosphines is found to occur with the generation of phospholes.