The first palladium-catalyzed Sonogashira coupling of amides has been developed, which proceeds via a selective cleavage of the N-acylsaccharin C-N bond. Notably, the new approach employs N-acylsaccharins as coupling partners to give ynones in good to excellent yield. This protocol can be efficiently utilized in the synthesis of a broad array of ynones under low catalyst loading and Cu-free conditions.

A rhodium-catalyzed C-H functionalization with activated amides by decarbonylation has been developed. Notably, this is the first C-H arylation employing N-acylsaccharins as coupling partners to give biaryls in good to excellent yields. The highlight of the work is the high tolerance of functional groups such as formyl, ester, and vinyl and the use of a removable directing group.

Ap alladium-catalyzed cross-coupling of activated amides with arylboronic acids has been developed via C-N bond cleavage.T his approach demonstrated high tolerance to av ariety of alkyl, aryl, heterocyclic and vinyl substituents.U nsymmetrical ketones could be achieved in excellent yield under mild conditions with 1% catalyst loadings.Scheme 2. Scope of boronic acids in the cross-coupling of amides.Scheme3.Scope of amides in the cross-couplingw ith boronic acids.Scheme4.Control reactions.

A highly efficient one-pot transamidation of primary amides has been developed under transition-metal free conditions, generating a variety of amides including hindered amides in good yield (up to 86%) catalyzed by CsF.