Photocatalytic C(sp<sup>3</sup>)–P and C(sp<sup>2</sup>)–P Bond Formation via a Phosphorus Radical Cation
Kui Zhang, Jie Liu, Yan Li, Yi‐Wei Xu, Lingchao Cai
Abstract
A straightforward method for the phosphorylation of electron-deficient alkenes and aryl alkynes has been developed, leading to C(sp 3 )–P and C(sp 2 )–P bond formation. This process involves the generation of phosphorus radical cation intermediates through the photocatalyzed oxidation of ethyl diarylphosphinites. The coupling with electron-deficient alkenes encompasses a variety of heteroaromatics, including pyridine, (benzo)thiazole, and benzoxazole, as well as α,β-unsaturated esters and amides. Impressively, the coupling of radical cations with aryl alkynes demonstrated remarkable regioselectivity, thereby facilitating the synthesis of rare α-aryl vinyl phosphine oxides.
Topics & Concepts
ChemistryPhosphorusPhotocatalysisPhosphorus-32RadiochemistryMedicinal chemistryOrganic chemistryCatalysisBiochemistryGeneNucleotideRadical Photochemical ReactionsSulfur-Based Synthesis TechniquesFluorine in Organic Chemistry