An electrochemical three component cascade phosphorylation reaction of various heteroatoms-containing nucleophiles including carbazoles, indoles, phenols, alcohols, and thiols with Ph 2 PH has been established. Electricity is used as the "traceless" oxidant and water and air are utilized as the "green" oxygen source. All kinds of structurally diverse organophosphorus compounds with P(O)-N/P(O)-O/P(O)-S bonds are assembled in moderate to excellent yields (three categories of phosphorylation products, 50 examples, up to 97 % yield). A tentative free radical course is put forward to rationalize the reaction procedure.

We report a direct and green electrochemical oxidative cross-dehydrogenative coupling reaction of N-heterocycles with hydrogen phosphoryl compounds under external oxidant-free conditions. Various phosphorylation products of substituted carbazoles and indoles are assembled in modest to excellent yields. A hydrogen release process is preliminarily demonstrated and H 2 is the sole byproduct. An imidazolium based ionic liquid is selected as the optimal electrolyte.

Herein, we report the development of transition‐metal‐catalyst‐ and external‐oxidant‐free electrochemical cross‐coupling hydrogen‐evolution chemistry involving glycine amides and diarylphosphine oxides. A broad range of biologically active α‐aminophosphonates was obtained in moderate to good yields in a clean and sustainable manner. Moreover, the TBAB (tetrabutylammonium bromide) electrolyte was recycled four times without obvious loss of reaction activity. Moreover, this protocol was performed on the gram scale under slightly modified electrolytic conditions or in combination with continuous flow microreactor technology. Control experiments were used to disclose a possible free‐radical mechanism.