The tandem cyclization of olefinic carbonyls with easily accessible diselenides facilitated by electrochemical oxidation has been successfully developed, which provides an environmentally friendly method for the construction of C–Se and C–O bonds simultaneously.

An electrochemical oxidative difunctionalization of allyl alcohols for the synthesis of β-trifluoromethyl ketones is achieved through a 1,2-migration process. A series of β-trifluoromethyl ketones can be facilely obtained utilizing CF3SO2Na as a radical source, eliminating the use of metals and sacrificial chemical oxidants. Importantly, this protocol not only realizes aryl migration but also offers alkyl-migration products. Additionally, an electrochemically catalyzed ring expansion and gram-scale reaction demonstrated the synthetic usefulness of this protocol.

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.

A highly selective, environmentally friendly, and scalable electrochemical protocol for the construction of α-acyloxy sulfides, through the synergistic effect of self-assembly-induced C­(sp3)–H/O–H cross-coupling, is reported. It features exceptionally broad substrate scope, high regioselectivity, gram-scale synthesis, construction of complex molecules, and applicability to a variety of nucleophiles. Moreover, the soft X-ray absorption technique and a series of control experiments have been utilized to demonstrate the pivotal role of the self-assembly of the substrates, which indeed is responsible for the excellent compatibility and precise control of high regioselectivity in our electrochemical protocol.

Ethers (CÀO/S) are ubiquitously found in a wide array of functional molecules and natural products. Nonetheless, the synthesis of imino sulfide ethers, containing an N(sp 2 ) = C(sp 2 ) À O/S fragment, still remains a challenge because of its sensitivity to acid. Developed here in is an unprecedented electrochemical oxidative carbon-atom difunctionalization of isocyanides, providing a series of novel multisubstituted imino sulfide ethers. Under metal-free and external oxidant-free conditions, isocyanides react smoothly with simple and readily available mercaptans and alcohols. Importantly, the procedure exhibited high stereoselectivities, excellent functional-group tolerance, and good efficiency on large-scale synthesis, as well as further derivatization of the products.Scheme 1. Electrochemical oxidative difunctionalization of the unsaturated bonds.