Base metal catalyzed (De)hydrogenative formylation and methylation reactions utilizing carbon dioxide and methanol as C1 sources

Abstract

Exploiting earth-abundant, bio-compatible first-row transition metals in homogeneously catalysed hydrogenation and dehydrogenation reactions for the synthesis of diverse organic frameworks has emerged as an important area in academia and industry. Catalytic (de)hydrogenation reactions form the basis of the modern chemical industry and are atom-economical, green and sustainable approach towards several new environmentally benign transformations. Carbon dioxide and methanol serve as sustainable feedstock and cost-effective raw materials for the synthesis of fine and bulk chemicals. The utilization of CO2 and methanol as C1 building blocks for the formation of carbon–carbon, carbon–nitrogen bonds have gained considerable interest in organic synthesis. Particularly noteworthy is the synthesis of N-formylated, N-methylated, C-methylated products because these motifs are prevalent in a large number of biological molecules as well as value-added chemicals.In this review, we aim to provide an overview of homogeneous base metal catalysed formylation and methylation reactions using carbon dioxide and methanol as C1 sources based on hydrogenation and dehydrogenation strategies.