Exploiting single-electron transfer in Lewis pairs for catalytic bond-forming reactions

Abstract

A single-electron transfer (SET) between tris(pentafluorophenyl)borane (B(C₆F₅)₃) and <i>N</i>,<i>N</i>-dialkylanilines is reported, which is operative <i>via</i> the formation of an electron donor-acceptor (EDA) complex involving π-orbital interactions as a key intermediate under dark conditions or visible-light irradiation depending on the structure of the aniline derivatives. This inherent SET in the Lewis pairs initiates the generation of the corresponding α-aminoalkyl radicals and their additions to electron-deficient olefins, revealing the ability of B(C₆F₅)₃ to act as an effective one-electron redox catalyst.