Abstract: Visible-light-facilitated phosphorus radical reactions have been developed as a powerful and sustainable tool for the synthesis of various organophosphorus compounds. In general, these reactions require stoichiometric amounts of oxidants, and reductants, bases, and radical initiators, leading to uneconomical and complicated processes. Progress has been made over the past few years toward using reactions that proceed under eco-benign and mild reaction conditions. Furthermore, these reactions have broad functional group tolerance, with some facile and economical pathways. Herein, we summarize the discoveries and achievements pertaining to C–P bond formation through a visible light photocatalysis procedure with high atom economy, made by our group and other research groups. It was established that greener and more environmentally friendly approaches do not require an additional oxidant or base. Moreover, we have designed and synthesized a new type of P-radical precursor, which can take part in reactions without the requirement for any additional bases, oxidants, and additives. This breakthrough, pertaining to novel visible-light-induced transformations, will be discussed and a plausible mechanism is proposed, based on corresponding experiments and the literature.
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