C–P bonds are widely found in a great many bioactive compounds and functional molecules. Transition-metal-catalyzed dehydrogenative C–H/P–H cross-coupling plays a crucial part in C–P bond formation since it requires no pretreatment of substrates. Herein, we reported a Mn-catalyzed electrochemical intermolecular dehydrogenative cross-coupling between aryl C–H and diphenyl phosphine oxides. In undivided cells, a series of phosphorylation or diphosphorylation products could be obtained separately by adjusting the proportion of substrates. A catalytic amount of inexpensive Mn­(II) salt was used, and no external chemical oxidants were needed in this process. A kinetic isotope effect experiment suggested that the C–H activation was not the rate-determining step.

Cyclopentenes are common cores in many natural products, and in bioactive and functional molecules. However, their synthesis remains challenging in terms of harsh conditions, poor selectivity, prefunctionalization of the substrates, over‐reliance on volatile activating reagents and the use of noble metals. Herein, we develop an electrochemical mediator‐induced intermolecular selective (3+2) annulation of readily available alkenes and alkynes/alkenes, which provides a simple and efficient method for the synthesis of a library of decorated cyclopentenes and cyclopentanes. This protocol features high efficiency, mild reaction conditions, broad substrate scope, good functional group tolerance, and high regioselectivity. Potential applications are demonstrated by gram‐scale synthesis as well as the construction of structural diversity and complexity. A preliminary mechanistic investigation was performed, which indicated that an iodine radical and carbon radicals are involved in this transformation.

Due to the importance of chroman frameworks in medicinal chemistry, the development of novel synthetic methods for these structures are gaining increasing interest of chemists. Reported here is a new...

Cyclopentenes are common cores in many natural products, and in bioactive and functional molecules. However, their synthesis remains challenging in terms of harsh conditions, poor selectivity, prefunctionalization of the substrates, over-reliance on volatile activating reagents and the use of noble metals. Herein, we develop an electrochemical mediator-induced intermolecular selective (3+2) annulation of readily available alkenes and alkynes/alkenes, which provides a simple and efficient method for the synthesis of a library of decorated cyclopentenes and cyclopentanes. This protocol features high efficiency, mild reaction conditions, broad substrate scope, good functional group tolerance, and high regioselectivity. Potential applications are demonstrated by gram-scale synthesis as well as the construction of structural diversity and complexity. A preliminary mechanistic investigation was performed, which indicated that an iodine radical and carbon radicals are involved in this transformation.