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Applications of Acceptorless Dehydrogenation (AD) process for the synthesis of important heterocycles are discussed. The key features of AD process are the generation of more reactive carbonyl/imine compounds from alcohols/amines by the release of dihydrogen as a stoichiometric byproduct. In this review, we document recent advances in this field by using first row transition metal catalysts and easily accessible coupling partners, thus offering cost-effective access to different heterocyclic rings.