First-Row Transition-Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account.

The development of sustainable catalytic protocols that circumvent the use of expensive and precious metal catalysts and avoid toxic reagents plays a crucial role in organic synthesis. Indeed, the direct employment of simple and abundantly available feedstock chemicals as the starting materials broadens their synthetic application in contemporary research. In particular, the transition metal-catalyzed diversification of alcohols with various nucleophilic partners to construct a wide range of building blocks is a powerful and highly desirable methodology. Moreover, the replacement of precious metal catalysts by non-precious and less toxic metals for selective transformations is one of the main goals and has been paid significant attention to in modern chemistry. In view of this, the first-row transition metal catalysts find extensive applications in various synthetic transformations such as catalytic hydrogenation, dehydrogenation, and related reactions. Herein, we have disclosed our recent developments on the base-metal catalysis such as Mn, Fe, Co, and Ni for the acceptorless dehydrogenation reactions and its application in the C-C and C-N bond formation via hydrogen auto-transfer (HA) and acceptorless dehydrogenation coupling (ADC) reactions. These HA/ADC protocols employ alcohol as alkylating agents and eliminate water and/or hydrogen gas as by-products, representing highly atom-efficient and environmentally benign reactions. Furthermore, diverse simple to complex organic molecules synthesis by C-C and C-N bond formation using feedstock alcohols are also overviewed. Overall, this account deals with the contribution and development of efficient and novel homogeneous as well as heterogeneous base-metal catalysts for sustainable chemical synthesis.