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Abstract Organophosphines have garnered attention from many avenues ranging from agriculture to fine chemicals. One‐time use of phosphate resources has made sustainable use of phosphorus overall imperative. Hydrophosphination serves as an efficient method to selectively prepare P−C bonds, furnishing a range of phosphorus‐containing molecules while maximizing the efficient use of phosphorus. Since the first report in 1958, a wide array of catalysts have appeared for hydrophosphination, a reaction that is spontaneous in some instances. This review presents a representative view of the literature based on known catalysts through mid‐2022, highlighting extensions to unique substrates and advances in selectivity. While several excellent reviews have appeared for aspects of this transformation, this review is meant as a comprehensive guide to reported catalysts.more » « less
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