Unusual Radical ipso-Substitution Reaction of an Aromatic Methoxy Group Induced by Tris(trimethylsilyl)silane-AIBN or SmI2.

While conformationally favourable thiocarbamates bearing an aromatic methoxy group undergo intramolecular ipso-substitution of the methoxy group by treatment with tris(trimethylsilyl)silane (TTMSS) and AIBN, either conformationally flexible or favourable ketones easily cyclise into a five- or six-membered rings by treatment with SmI2.