Electrochemical analyses of 4,4,5,5-tetramethyl-2-phenylsulfanylmethyl-[ 1,3,2] dioxaborolane and tetra-n-butylammonium phenylthiomethyltrifluoroborate were comparatively studied by cyclic voltammetry measurements and we found for the first time the beta-effect of organoborate, which was indicated by experimental and theoretical aspects. The organoborate was found to have a much lower oxidation potential compared to the organoborane. Anodic substitution reaction of organoboronate ester and organoborate was successfully carried out in the presence of nucleophiles to afford the selectively substituted products in good yields. (C) 2016 Elsevier Ltd. All rights reserved.