General and Efficient C-P Bond Formation by Quantum Dots and Visible Light

Abstract

The photocatalytic C-P bond formation reaction involving phosphoryl radicals provides a powerful strategy in phosphorus chemistry. However, the engagement of the phosphoryl radical-forming reaction without stoichiometric oxidants or radical initiators has proven difficult. Herein, we report our discovery that semiconductor quantum dots can act as the sole catalyst to convert H-phosphine oxide into the phosphoryl radical under visible light irradiation. The radical species thus generated can be utilized to undergo radical addition with alkene or radical coupling with α-amino C-H bonds for C-P bond formation. A radical clock experiment and electron paramagnetic resonance spectroscopy identified the phosphoryl radical and α-amino alkyl radicals, responsible for the construction of valuable phosphorus-containing complexes without external oxidants or radical initiators in a step- and atomeconomical fashion.