Rearrangement of 2-Benzocycloammonium N-Methylides

2-Methyl-2-[(trimethylsilyl)methyl]-2,3,4,5,6,7-hexahydro-1H-2-benzazoninium iodide (9), 2-methyl-2-[(trimethylsilyl)methyl]-1,2,3,4,5,6-hexahydro-2-benzazocinium iodide (15), and 2-methyl-2-[(trimethylsilyl)methyl]-2,3,4,5-tetrahydro-1H-2-benzazepinium iodide (23) exist as mixtures of two stable conformational isomers (types A and B) in an aprotic solvent at room temperature. The corresponding conformational isomers of N-methylides 10A,B, 16A,B, and 24A,B were generated by fluoride ion-induced desilylation, and their rearrangement was investigated. Type A ylides gave [2,3] sigmatropic rearrangement products (isotoluenes) 11, 17, 18, and 27, while type B ylides gave Stevens rearrangement products 8, 20, and 29 via radical-cleavage and -recombination pathways.