Ring-opening olefin metathesis of twisted amides: Activation of amide bonds by cac cleavage

Selective Câ C bond cleavage in twisted amides by ring-opening olefin metathesis (ROM) was accomplished. The reaction represents the third mechanism for ring opening of nonplanar amide bonds discovered. Adding to the facile hydrolytic cleavage of nonplanar N-C(O) amide bonds and σ N-C bond scission reactions, this reaction manifold engages a peripheral reactivity principle that hinges upon ring strain energy enforced by the twisted amide bond. Considering the wide utility of ring-opening olefin metathesis reactions in various aspects of chemistry, we anticipate that this ring-opening methodology will be of broad interest and could lead to the development of ROM reactions of twisted amides as a powerful synthetic tool.