How to Make a Phosphine by Catalytic Hydrophosphination

After more than 10 years of increasingly aggressive interest, enough principles are understood such that catalytic hydrophosphination is a viable technique in the synthetic chemist’s toolbox. While there are still gaps in understanding, the technique is now sufficiently available for planned use in more complex syntheses. The key markers of highly active hydrophosphination are explored with an eye toward use in new venues, and current limitations are described as an invitation for future discovery. For new users to hydrophosphination, a guide to general catalysts that provide conversion for a given pair of substrates is provided. For investigators in the field, a call to transition from the de facto benchmark substrate styrene to a more challenging benchmark substrate, such as 1‐hexene, is proposed as well as a call to discontinue exploratory catalysis on highly activated substrates like Michael acceptors.