A Practically Unified Electrochemical Strategy for Ni-Catalyzed Decarboxylative Cross-Coupling of Aryl Trimethylammonium Salts

Abstract

By merging electrocatalysis and nickel catalysis, a unified strategy has been successfully applied to achieve the decarboxylative crosscoupling of four types of α-oxocarboxylic acids and their derivatives with aryl trimethylammonium salts under mild conditions. Our strategy provides a practical way for preparing aryl ketones, amides, esters, or aldehydes.

Cobalt‐Catalyzed Deaminative Amino‐ and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light

“…[12] We next applied our catalytic system to a diverse set of aryl trialkylammonium salts (Figure 2). Aminocarbonylations of electronically varied substrates proceeded in good to excellent yields (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11). This reaction can also be performed on gram scale, as demonstrated with trialkylammonium salt 1 (70 % isolated yield).…”

“…Catalytic cross‐couplings of aryl trialkylammonium salts have been known for decades, with a wide range of synthetically attractive variants developed, [3] including the formation of carbon–carbon [3b–f] and carbon–heteroatom [3g–i] bonds, reductive reactions, [3j–k] and C−H functionalizations [3l–m] . Aryl trialkylammonium salts have also recently been used to access benzamides via nickel catalyzed electrochemical cross‐coupling [4] . In contrast, despite the high value of C(sp 2 )−X carbonylation of (hetero)aryl electrophiles in synthesis, carbonylations of aryl trialkylammonium salts via C(sp 2 )−N activation remain unknown (Figure 1).…”

“…[3l-m] Aryl trialkylammonium salts have also recently been used to access benzamides via nickel catalyzed electrochemical cross-coupling. [4] In contrast, despite the high value of C(sp 2 )À X carbonylation of (hetero)aryl electrophiles in synthesis, carbonylations of aryl trialkylammonium salts via C(sp 2 )À N activation remain unknown (Figure 1). While carbonylations of diazonium salts have been reported, [5] these highly reactive electrophiles are not generally suitable in aminocarbonylation catalysis, owing to their high reactivity with common nucleophiles such as amines.…”

Recent Advances in the Nickel‐catalysed Electrochemical Coupling Reactions with a Focus on the Type of Bond Formed

“…In 2022, Kong et al developed an electrochemical strategy to achieve the decarboxylative cross-coupling of aryl trimethylammonium salts with α-oxocarboxylic acids and their derivatives, namely, 2-Oxocarboxylic acids, N,N-Disubstituted oxamic acids, Potassium oxoacetates, Glycolic acid monohydrates under mild conditions (Scheme 21). [41] The optimized reaction was obtained by using an undivided cell of Carbon anode and Nifoam cathode under a constant electric current of 12 mA with NiBr 2 as the catalyst, 4,7-diphenyl-1,10-phenanthroline as ligand, n-Bu 4 NBF 4 as supporting electrolyte, NaOAc as a base, CH 3 CN:DMF (1 : 4) as the solvent in an inert atmosphere of N 2 for 6 hours. This approach can be easily scaled up for synthesizing aryl aldehydes, ketones, esters and amides possessing various functional groups.…”

Manganese-mediated reductive N,N-dialkylation of nitroarenes: a dramatic NiI2 effect

“…Taking these aspects into consideration, coupled with our interest in radical chemistry, 13 herein, we report a radical-mediated practical method for the efficient construction of N , N -dialkyl anilines via reductive dialkylation of cheap nitro(hetero)benzenes using manganese powder as the terminal reductant (Fig. 2C).…”