Electrochemical Nozaki–Hiyama–Kishi Coupling: Scope, Applications, and Mechanism

Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination of triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light–emitting diodes can catalyze the alkylation of silyl enol ethers by decarboxylative coupling with redox-active esters in the absence of transition metals. Deaminative alkylation using Katritzky’s N-alkylpyridinium salts and trifluoromethylation using Togni’s reagent are also demonstrated. Moreover, the phosphine/iodide-based photoredox system catalyzes Minisci-type alkylation of N-heterocycles and can operate in tandem with chiral phosphoric acids to achieve high enantioselectivity in this reaction.

This edition is fully revised to reflect the current state off the field.<br>* Significant additions include ultramicroelectrodes, modified electrodes, and scanning probe methods.<br>* Many chapters have been modified and improved, including electrode kinetics, voltammetric methods, and mechanisms of coupled chemical reactions.