Current-controlled nickel-catalyzed multi-electrophile electroreductive cross-coupling

Abstract

The electroreductive cross-electrophile coupling which is emerged as a powerful, green and efficient method for constructing challenging C-C bonds has attracted increasing attention of organic chemists. Most of previous works...

When transition-metal catalysis meets electrosynthesis: a recent update

“…In terms of nickel-electrocatalytic three-component reductive cross-electrophile coupling, Bai, Shi and co-workers described a three-electrophile coupling between alkyl chlorides, propyl chloroformate, and aryl iodides (Scheme 29). 85 This electro-reductive protocol represents a sustainable platform to prepare alkyl aryl ketones from easily accessible substrates. The use of propyl chloroformate as the CO precursor obviates the need for CO gas or toxic metal carbonyl complexes and encourages future development of new carbonylative cross-electrophile coupling reactions.…”

Recent Advances in Electrochemical, Ni‐Catalyzed C−C Bond Formation

“…Bai, Shi, and co‐workers reported a 3‐component reaction with aryl iodides, propyl chloroformate (as a CO source), and benzyl chlorides/alkyl iodides (Figure 37). [84] The reaction proceeds under constant current (15 mA, 8.3 mA/cm 2 ) with a sacrificial Zn anode to form alkyl aryl ketones. For alkyl iodides, a mixture of DMA/dioxane (4:2) is used and 3 equivalents of KF is added.…”

Electrochemically driven cross-electrophile esterification of alkyl halides

“…The controllable electron transfer between the cathode and the nickel catalyst offers a significant advantage for cross-electrophile coupling reactions, as electrochemical reduction can replace chemical reduction, thereby eliminating the need for stoichiometric reductants. [31][32][33][34][35][36][37][38][39][40][41] Therefore, electroreductive transition-metal catalyzed cross-electrophile coupling has attracted increasing attention from organic chemists (Fig. 1a).…”

“…1b). Inspired by the pioneering studies and our reductive carbonylation studies with ClCO 2 R as a CO source, [40][41][42][43][44] we hypothesize a novel electrochemically driven cross-electrophile esterification approach that effectively circumvents the issues associated with decarbonylation and catalyst loading. By precisely controlling the electron transfer from the cathode to the substrate through adjustments in potential and current, we enable the direct electrochemical activation of organic halides, yielding a carbanion equivalent in the form of an organometallic reagent.…”