Harnessing the Power of the Water‐Gas Shift Reaction for Organic Synthesis

Since its original discovery over a century ago, the water‐gas shift reaction (WGSR) has played a crucial role in industrial chemistry, providing a source of H₂ to feed fundamental industrial transformations such as the Haber–Bosch synthesis of ammonia. Although the production of hydrogen remains nowadays the major application of the WGSR, the advent of homogeneous catalysis in the 1970s marked the beginning of a synergy between WGSR and organic chemistry. Thus, the reducing power provided by the CO/H₂O couple has been exploited in the synthesis of fine chemicals; not only hydrogenation‐type reactions, but also catalytic processes that require a reductive step for the turnover of the catalytic cycle. Despite the potential and unique features of the WGSR, its applications in organic synthesis remain largely underdeveloped. The topic will be critically reviewed herein, with the expectation that an increased awareness may stimulate new, creative work in the area.