LDA-promoted decomposition of benzenesulfenamides. A route to aminyl radicals by dioxygen oxidation of lithium amides
作者:Anna Barbieri、Pier Carlo Montevecchi、Daniele Nanni、Maria Luisa Navacchia
DOI:10.1016/0040-4020(96)00799-5
日期:1996.10
The LDA-promoted decomposition of N-monosubstituted sulfenamides 1a-d occurs through the formation of thioaminyl anions, which undergo oxidation either at sulfur, with formation of sulfonamides, or at nitrogen, with formation of thioaminyl radicals, depending on the nature of the 4′-substituent. The reaction of N,N-disubstituted sulfenamides 1e-h proceeds through the intermediacy of a lithium complex
Intermediates in the reaction of N,N-dimethylanilines with palladium (II) acetate were trapped by acetate ion or oxygen to give N-methyloxygenated and demethylated products, while the trapping by other anilines gave homo- and cross-coupling cyclodimers. The reactions proceed via radical cation formation induced by the palladium salt.