The Barbier–Grignard‐Type Arylation of Ketones and Unexpected Cross‐Coupling of Phenolic Ketones using Unactivated Aryl Bromides

Abstract

A novel, highly versatile and efficient method has been developed for the Barbier–Grignard‐type arylation of ketones and an unexpected cross‐coupling of phenolic ketones was observed using unactivated bromides and magnesium in tetrahydrofuran/toluene at 96 °C promoted by multicatalysts of cupric bromide (15 mol%), bismuth chloride (5 mol%) and silver bromide (10 mol%). The substituent and electronic effects on the reaction have been discussed. High yields of arylation and cross‐coupling have been attained under mild conditions. A novel reasonable mechanism involving a quinone intermediate is proposed. The high chemical selectivity in the cross‐coupling to the hydroxy group of phenolic ketones should help ketones find new applications.magnified image

The introduction of the Barbier reaction into polymer chemistry

“…Introducing small molecular carbon–carbon bond formation reactions to polymer synthesis has become a desirable goal for polymer chemists because it greatly expands the structure and property library of polymeric materials. The Barbier reaction 18 – 22 , an organic reaction for carbon–carbon bond formation through metal-mediated addition of an organic halide to a carbonyl compound as an electrophilic substrate, has been widely used in organic chemistry since 1899. In comparison with the analogous Grignard reaction, the Barbier reaction benefits from tolerance to functional groups and moisture, widely applicable metals and one-pot preparation.…”

Synthesis of 1H‐Indazoles and Quinazolines Using Additive Intermediates of Grignard Reagents to 2‐Amino Benzonitriles

“…But the carbonyl group in the used esters or amide intermediate 10 a are less reactive than that in DMF. Thus, we suggest the synthesis of quinazolines in this paper could be promoted by the interaction of BiCl 3 /PPh 3 to the carbonyl groups in the used ester and amide intermediate 10 a , which could be supported by the BiCl 3 /PPh 3 catalyzed Barbier‐Grignard reaction of bromobenzene with aldehydes . Based on these results, a plausible reaction mechanism has been proposed in Scheme .…”

“…When 10 mol% of FeCl 3 and 10 mol% of Bpy were employed, the yield of reaction was reduced to 72%. Temperature of 103 °C (reflux temperature of the mixing solvents revealed in our former works) is the highest reaction temperature in favor of forming Grignard reagent and 1H‐indazoles (yield of 67% was obtained at 90 °C). Reaction time was confirmed by observation of disappearance of additive intermediates (2‐aminoketoimines) using TLC plate.…”

A Simple and Efficient Synthesis of Tertiary Alcohols via Ta2O5- Catalyzed Barbier-Grignard Addition of Unactivated Aryl Bromides to Aryl Acids

“…75～77 ℃(文献值 m.p. 70～71 ℃); 1 H NMR (300 MHz, CDCl 3 ) δ: 7.32 (s, 5H), 7.17 (d,J＝5.8 Hz,8H), 2.78 (s, 1H), 2.38 (s, 6H); IR (KBr) ν: 3471,3056,2918,1508,1445,1152,1008,814,752,723, 602 cm -1 ; MS (EI) m/z: 288 (M ＋ ), 211, 119, 105, 91, 77.…”

“…44～46 ℃(文献值 m.p. 46～47 ℃); 1 H NMR (300 MHz, CDCl 3 ) δ: 7.63～7.00 (m, 10H), 2.93 (dt, J＝13.4, 6.7 Hz, 1H), 2.08 (s, 1H), 0.93 (d,J＝6.7 Hz,6H); IR (KBr) ν: 3583,2970,1466,1162,1008,757,701, 632 cm -1 ; MS (EI) m/z: 226 (M ＋ ), 183, 165, 105, 77, 91. 辅助材料(Supporting Information) 所合成已知化合 物的 1 H NMR 和 GC/MS 谱图; 新化合物的 1 H NMR, 13 C NMR 以及高分辨质谱(HRMS)谱图. 这些材料可以免费 从本刊网站(http://sioc-journal.cn/)上下载.…”