Broken Promises? On the Continued Challenges Faced in Catalytic Hydrophosphination

[Image: see text] In this Perspective, we discuss what we perceive to be the continued challenges faced in catalytic hydrophosphination chemistry. Currently the literature is dominated by catalysts, many of which are highly effective, that generate the same phosphorus architectures, e.g., anti-Markovnikov products from the reaction of activated alkenes and alkynes with diarylphosphines. We highlight the state of the art in stereoselective hydrophosphination and the scope and limitations of chemoselective hydrophosphination with primary phosphines and PH(3). We also highlight the progress in the chemistry of the heavier homologues. In general, we have tried to emphasize what is missing from our hydrophosphination armament, with the aim of guiding future research targets.