1,5‐X Insertions of Free Alkylidene Carbenes: A Theoretical Study

Abstract 1,5‐X insertions of alkylidene carbenes are powerful methods to construct five‐membered carbocycles and heterocycles, but the mechanisms of these 1,5‐X insertions of alkylidene carbenes remain unclear (concerted or stepwise?). Here we disclose different mechanisms of 1,5‐X insertions of free alkylidene carbenes based on DFT calculations. Except for the 1,5 S−H insertion, all 1,5‐X insertions proceed through stepwise processes via forming ylide intermediates. However, subsequent 1,2 rearrangements of ylides occur through different mechanisms. The formal 1,5 O−H/N−H insertion except S−H insertion happens through deprotonation rather than insertion reaction, while other pathways including nucleophilic substitution, 2,3‐sigmatropic rearrangement, and homolysis of O−C bond are invoked in various 1,5 O−C insertions. The competition between 1,5‐X insertions and other side reactions (such as 1,2 migration, dealkylation) has been discussed to answer why the target insertion products were not obtained in some cases.