Silyl Radical Cascade Cyclization of 2-Isocyanothioanisole toward 2-Silylbenzothiazoles through Radical Initiator-Inhibitor Symbiosis.

A demethylative silyl radical cascade cyclization of 2-isocyanothioanisoles toward 2-silylated benzothiazole building blocks has been developed. The development of a "radical initiator-inhibitor symbiosis" system solves the challenge of otherwise dominant methyl radical-triggered side reactions brought about by kinetically unfavored generation of reactive silyl radical species. The products accessed in this protocol are amendable to various downstream functionalization reactions, including the quick construction of a topoisomerase II inhibitor via a Hiyama cross-coupling reaction and of an antiviral agent via a fluoride-/hydroxide-free nucleophilic substitution to acyl chloride.