Comparative DFT study of metal-free Lewis acid-catalyzed C–H and N–H silylation of (hetero)arenes: mechanistic studies and expansion of catalyst and substrate scope

Direct selective dehydrogenative silylation of thiophenes, pyridines, indoles and anilines to synthesize silyl-substituted aromatic compounds catalyzed by metal-free Lewis acids was achieved recently. However, there is still insufficient mechanistic data for these transformations. Using density functional theory calculations, we conducted a detailed investigation of the mechanism of the B(C(6)F(5))(3)-catalyzed dehydrogenative silylation of N-methylindole, N,N-dimethylaniline and N-methylaniline. We successfully located the most favourable reaction pathways that can explain the experimental observations notably well. The most favourable pathway for B(C(6)F(5))(3)-catalyzed C–H silylation of N-methylindole includes nucleophilic attack, proton abstraction and hydride migration. The C–H silylation of N,N-dimethylaniline follows a similar pathway to N-methylindole rather than that proposed by Hou's group. Our mechanism successfully explains that the transformations of N-methylindoline to N-methylindole produce different products at different temperatures. For N-methylaniline bearing both N–H and para-phenyl C–H bonds, the N–H silylation reaction is more facile than the C–H silylation reaction. Our proposed mechanism of N–H silylation of N-methylaniline is different from that proposed by the groups of Paradies and Stephan. Lewis acids Al(C(6)F(5))(3), Ga(C(6)F(5))(3) and B(2,6-Cl(2)C(6)H(3))(p-HC(6)F(4))(2) can also catalyze the C–H silylation of N-methylindole like B(C(6)F(5))(3), but the most favourable pathways are those promoted by N-methylindoline. Furthermore, we also found several other types of substrates that would undergo C–H or N–H silylation reactions under moderate conditions. These findings may facilitate the design of new catalysts for the dehydrogenative silylation of inactivated (hetero)arenes.