Autoxidative C(sp 2)–P Formation: Direct Phosphorylation of Heteroarenes under Oxygen, Metal-Free, and Solvent-Free Conditions

We reveal here a direct autoxidative phosphorylation of heteroarenes induced by oxygen under metal-free and solvent-free conditions. This new methodology provides an economical, operationally simple, and environmentally friendly approach toward (Het)­C­(sp 2)–P formation with medium to excellent yields. Heteroarenes including thiazole and quinoxaline derivatives are applicable under standard conditions, which is testified via a radical mechanism.