Nickel-catalyzed carbonylation of arylboronic acids with DMF as a CO source

Abstract

By using N,N-dimethylformamide (DMF) as a CO source, nickel-catalyzed carbonylation of arylboronic acids was demonstrated as an efficient and facile protocol for the synthesis of diaryl ketones.

DMF as CO Surrogate in Carbonylation Reactions: Principles and Application to the Synthesis of Heterocycles

“…More recently, a different nickel-catalyzed carbonylative reaction was reported: Lu, Liu and co-workers described the carbonylative homo-coupling of aryl boronic acids 30 with DMF as a CO surrogate. [39] Interestingly, in the optimization of the experimental conditions Scheme 11. Simplified proposed reaction mechanism for the Ni-catalyzed aminocarbonylation of aryl iodides/bromides 25, using DMF as the source of CO and N,N-dimethylamino groups, reported in 2007 by Lee and co-workers [37].…”

“…More recently, a different nickel-catalyzed carbonylative reaction was reported: Lu, Liu and co-workers described the carbonylative homo-coupling of aryl boronic acids 30 with DMF as a CO surrogate [39]. Interestingly, in the optimization of the experimental conditions several metals have been tested, including FeCl 3 , CuCl 2 and CoCl 2 , but no reaction occurred; among nickel species, the best conditions were obtained in the presence of NiBr 2 •diglyme (5 mol%) as catalytic precursor and bis(2,6-diisopropylphenyl)imidazol-2-ylidene hydrochloride (10 mol%) as a ligand.…”

Recent Uses of N,N-Dimethylformamide and N,N-Dimethylacetamide as Reagents

“…A carbonylative Suzuki-type reaction leading to diarylketones arose in DMF under Ni catalysis at 100 °C (Equation (55)), IPr = bis(2,6-diisopropylphenyl)imidazol-2-ylidene) [ 13 ], or Pd catalysis and UV light assistance at room temperature (Equation (56)) [ 68 ].…”

“…When uncertainty is expressed by the authors or suspected by us, the atom is typed in italic. Mechanistic schemes are not reported, but Scheme 2 [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ] summarizes different proposed reactions of DM with the corresponding literature references, where DM acts as either a nucleophilic or electrophilic reagent, or leads to neutral, ionic or radical species. The review is divided in Sections depending on the DM fragment(s) which is (are) incorporated into the reaction product.…”

N,N-Dimethylformamide: An Versatile Organic Synthetic Reagent

“…反应原料中苯环上取代基具有较好的 相 容 性 , 除 了 甲 基 和 醚 外 , 卤 素 取 代 也 是 允 许 的 (Scheme 3). 后来, 该团队 [9] 在高压釜内以 Pd/C 催化 DMF 分解产生 CO 气体进行羰基化反应, 合成产物 11H-吡啶并 [2,1b] [10] , 产物的产率为 52%～ 92%. Scheme 7 为该反应可能的反应机理.…”