A sustainable metal-free and additive-free olefination route to -heteroazaarenes from methyl-substituted heterocycles and amines.

A green and sustainable metal-free, additive-free olefination approach is proposed for the facile synthesis of various unsaturated -heteroazaarenes from simple methyl-substituted heteroarenes and amines. The developed protocol employs only air as the sole oxidant and provides a useful strategy for obtaining various -selective conjugated heterocyclic olefins. This provides a useful strategy for application in generating grams of a variety of unsaturated -heteroazaarenes (up to 20.33 grams) and the synthetic imaging agents of STB-8 (2.40 gram) with high regioselectivity in one pot.