Catalytic dehydrogenative synthesis of α,β-unsaturated secondary amides without external oxidants.

Direct dehydrogenative synthesis of α,β-unsaturated secondary amides still represents an elusive transformation. Herein we describe a palladium-catalyzed redox-neutral desaturation to prepare α,β-conjugated secondary amides. Without external oxidants, this approach relies on the N-O bond cleavage as the driving force to achieve formal dehydrogenation. Complementary to known protocols, this transformation is enabled by the unique reactivity of hydroxamate, thereby representing a novel strategy to accomplish carbonyl desaturation. Desired conjugated secondary amides can be efficiently synthesized in the presence of more reactive esters and even ketones, thus providing a solution to the long-standing issue of α,β-unsaturated secondary amides via C-C desaturation.