General Anti-Markovnikov Hydrophosphinylation of Olefins Using Disulfide as the Photocatalyst and a Hydrogen Atom Shuttle

The photoinduced radical-based hydrophosphinylation suffered from substrate scope limitation due to the highly electrophilic property of the P(O) radical. Herein, we report an efficient catalytic system for the intermolecular anti-Markovnikov hydrophosphinylation of olefins using disulfide as a photocatalyst and also a hydrogen atom shuttle. This metal-free, base-free, and redox-neutral condition allowed the alkenes with diverse electronic properties to proceed with the anti-Markovnikov P–H addition efficiently. A plausible mechanism involving the HAT process between ArS• and P(O)–H was proposed.