The Stille Reaction, 38 Years Later

The first now-named Stille reaction was published 38 years ago, and the last comprehensive revision of this catalysis was in 2004. Since then, the knowledge of the different steps of the three possible (and sometimes competing) reaction pathways (cyclic, open, and ionic) has been almost completed by synergistic experimental and theoretical studies: the Stille reaction is perhaps the best characterized catalytic process if we consider the number of intermediates that have been detected. This review concentrates on the mechanistic new knowledge and on important aspects such as the revolution with the use of bulky phosphines, the bimetallic alternative of the Stille reaction, the enantioselectivity in Stille and palladium-free Stille processes, the meaning of copper effect, or the possible approaches to make Stille coupling a greener process.