An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell in an atom‐economic fashion. The protocol relies on tandem cyclization of N‐cyanamide alkenes by using Langlois’ reagent as a source of both CF3 and SO2 under direct anodically oxidative conditions, in which two C−C bonds, two C−X bonds (N−S and S−C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N‐sulfonylimines from readily accessible materials.

The activation of carbon dioxide mediated by the first row 3d transition metal (TM) M atomic ions was studied theoretically. Theoretical calculations show left-hand transition-metal ions Sc, Sc, Ti, Ti, and V can mediate oxygen atom transfer (OAT) from carbon dioxide. In the anionic system, for early transition metal ions (Sc to Cr), [OM-CO] are more stable than [M-OCO], while the others favor binding formation, [M-OCO]. TSR was observed in O atom transfer. The OAT reaction is exothermic only for the first three transition metal cations and atoms (Sc, Ti, and V), Fe and all the anions except Cu and Zn. Furthermore, in most case, reaction enthalpy, and energy barrier of OAT for the cationic system is the highest, and the anionic system is the lowest. We discuss the performances of 18 methods on the energies and structures.

A copper-catalyzed alkene-trifluoromethylation-triggered nitrile insertion/remote functionalization relay process has been achieved, in which “interrupted” remote 1,n-difunctionalizations of alkenes with nitrile insertion can deliver iminyl radical intermediates instead of C-based radicals, followed by subsequent 1,n-HAT to furnish corresponding remote functionalization. This relay protocol enables a straightforward approach to streamline the assembly of structurally diverse trifluoromethylated azaheterocycles.

An unprecedented electrochemical trifluoromethylation/SO 2 insertion/cyclization process has been achieved in an undivided cell in an atom-economic fashion. The protocol relies on tandem cyclization of N-cyanamide alkenes by using Langlois reagent as a source of both CF 3 and SO 2 under direct anodically oxidative conditions, in which two C À C bonds, two C À X bonds (N À S and S À C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N-sulfonylimines from readily accessible materials.

An electrochemical three-component transformation between N-cyanamide alkene, Na2S2O5 and sulfonyl hydrazide was described, in which various sulfonylated fused sultams were prepared in a sustainable and modular fashion. In this process,...