CHEMOSELECTIVE INTRAMOLECULAR AMINOCARBONYLATION OF UNSATURATED AMIDES UNDER WACKER-TYPE CONDITIONS

The Wacker-type aminocarbonylation of unsaturated amides shows distinc tive dependence of reactivity on the reaction medium: endo nitrogen nu cleophiles (endo-carbamates 3 and-ureas 5) undergo aminocarbonylation either in neat methyl orthoacetate (MOA) or in methanol containing AcO Na and MOA, while exo nitrogen nucleophiles (exo-carbamates 1a, -ureas 1b, and sulfonamides 1c) in methanol (cat. PdCl2, stoichiometric CuCl 2 under 1 atm of CO). The generality is indicated by the chemoselectiv e transformations of 7a-d either into 8a-d in MOA or into 9a-d in meth anol. Copyright (C) 1996 Elsevier Science Ltd