Abstract
Significance: It seems opportune to accompany the present revival of synthetic organic electrochemistry by drawing attention of synthetic chemists to the heterogeneous nature of electrochemical reactions. Quantitative analysis of the successive layers in between working electrode and solution––electrical double layer, forced convection–diffusion layer, and reaction–diffusion layers––allows the mastering of the relationships between mechanism and product selectivity. The multiple connections between catalysis and electrochemical reactions are emphasized and illustrated by typical examples. Advantage is taken of the recent advances in activation of small molecules in response to modern energy and environment challenges with extension to synthetic organic electrochemical reactions.

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