LDA-PROMOTED DECOMPOSITION OF BENZENESULFENAMIDES - A ROUTE TO AMINYLRADICALS BY DIOXYGEN OXIDATION OF LITHIUM AMIDES

The LDA-promoted decomposition of N-monosubstituted sulfenamides 1a-d occurs through the formation of thioaminyl anions, which undergo oxida tion either at sulfur, with formation of sulfonamides, or al nitrogen, with formation of thioaminyl radicals, depending on the nature of the 4'-substituent. The reaction of N,N-disubstituted sulfenamides 1e-h p roceeds through the intermediacy of a lithium complex capable of gener ating aminyl radicals via sulfenyl group transfer to the di-iso-propyl amido anion and subsequent aerial oxidation of the resulting lithium a mides 3e-h. Copyright (C) 1996 Published by Elsevier Science Ltd.