This manuscript reviews for the first time developments at the interface between organic electrosynthesis and single-atom catalysis, highlighting advantages in shifting from a batch to a flow production.

Recognizing and classifying the recently appeared reactivity enabling unconventional solvents is the main objective of this tutorial review, for applications in the field of C–H bond functionalization reactions.

Described here is a synthetic approach to access two of the most widely invoked cationic cobaltacycles in Cp*Co -catalyzed C-H functionalization reactions by C-H activation. The unique stabilizing capability of MeCN was used to surmount the previously proposed reversible nature of the C-H metalation step. Moreover, it is revealed the boosting effect of 1,1,1,3,3,3-hexafluoroisopropanol in the metalation step and in the reaction between N-pyrimidinylindole and diphenylacetylene under catalytic conditions.