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

Thephotoinduced radical-based hydrophosphinylation suffered from substrate scope limitation due to the highly electrophilic propertyof the P(O) radical. Herein, we report an efficient catalytic systemfor the intermolecular anti-Markovnikov hydrophosphinylation of olefinsusing disulfide as a photocatalyst and also a hydrogen atom shuttle.This metal-free, base-free, and redox-neutral condition allowed thealkenes with diverse electronic properties to proceed with the anti-MarkovnikovP-H addition efficiently. A plausible mechanism involving theHAT process between ArS & BULL; and P(O)-H was proposed.

Automated summary

Here, we demonstrate an efficient catalytic system for the intermolecular anti-Markovnikov hydrophosphinylation of olefins using disulfide as a photocatalyst and a hydrogen atom shuttle. This metal-free, base-free, and redox-neutral condition allows alkenes with diverse electronic properties to efficiently proceed with the anti-Markovnikov P-H addition. A plausible mechanism involving the hydrogen atom transfer process between ArS and P(O)-H is proposed.