Cobalta‐Electrocatalyzed C−H Activation in Biomass‐Derived Glycerol: Powered by Renewable Wind and Solar Energy

Abstract

Aqueous glycerol was identified as a renewable reaction medium for metalla‐electrocatalyzed C−H activation powered by sustainable energy sources. The renewable solvent was employed for cobalt‐catalyzed C−H/N−H functionalizations under mild conditions. The cobalta‐electrocatalysis manifold occurred with high levels of chemo‐ and positional selectivity and allowed for electrochemical C−H activations with broad substrate scope. The resource economy of this strategy was considerably substantiated by the direct use of renewable solar and wind energy.

C–H Activation: Toward Sustainability and Applications

“… 90 , 134 − 139 In a recent protocol, a challenging C–C/C–N bond formation with a potentially sensitive allene was accomplished under mild conditions in the biosolvent glycerol using simple Co(OAc) 2 salt ( Scheme 34 A). 140 Furthermore, electricity generated in house from wind and solar energy was exploited. Building on Ackermann’s earlier work, Lei and co-workers used electrochemistry for the amination of (hetero)arenes including aryls, furans, and thiophenes, up to gram scale ( Scheme 34 B).…”

Evolution of High‐Valent Nickela‐Electrocatalyzed C−H Activation: From Cross(‐Electrophile)‐Couplings to Electrooxidative C−H Transformations

“…While these approaches have largely exploited chelation-assistance, [61a] recentp rogress was made towardse lectrocatalyzed CÀHa ctivations without directing groups. [61b] In consideration of the environment-friendly nature of nickela-electrocatalytic oxidations, further excitingd evelopments are expected in this rapidlye volving research arena, such as the direct use of renewable forms of energy, [62] C(sp 3 )À Ha ctivations, CÀHa lkylations, [63] or particularlye nantioselective electrochemical-transformations. [64]…”

Contribution to the production and use of biomass-derived solvents – a review

“…Several other studies demonstrate the application of glycerol as a viable solvent in synthesis processes [24,30]. A reaction aqueous medium containing glycerol was used by Meyer et al [31] for metallaelectro-catalyzed C H activation. Usually, this reaction is made by applying costly and toxic oxidants, besides that fossil-derived compounds as showed in C H/N H alkyne annulation [32].…”

“…Usually, this reaction is made by applying costly and toxic oxidants, besides that fossil-derived compounds as showed in C H/N H alkyne annulation [32]. So, in the Meyer et al [31], the authors performed the same reaction using glycerol that has a better conductivity in relation to other usual solvents such as of this reaction. In Fig.…”