Recent Progress in Pd-Catalyzed Decarboxylative Coupling Reactions of (Hetero)aromatic Carboxylic Acids

Abstract

Since carboxylic acids have distinguishing features of non-toxicity, low cost, ready availability and easy storage, Pd-catalyzed decarboxylative coupling reactions of (hetero)aromatic carboxylic acids have been obtained rapid development since this century, and have exhibited a tendency toward replacement of traditional coupling reactions. The coupling reactions of Pd-catalyzed decarboxylation of aromatic carboxylic acids with various substrates of olefins, aryl halides, arenes, aryltrifluoroborates and etc. are reviewed, and the relevant reaction mechanisms are discussed.

Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions

“…Under transition-metal catalysis, the decarboxylative reaction only takes place at a neighboring position to the carboxyl group with high regioselectivity and releases innocuous carbon dioxide as sole byproduct. Hence, carboxylic acids and transition-metal-catalyzed decarboxylative reactions have displayed promising strategies to create C–X and C–C bonds during the past decade . In this field, Myers, Goossen, and Forgione have done some seminal studies to generate new C–C bonds through transition-metal-catalyzed decarboxylative coupling of (hetero)­aromatic carboxylic acids with alkenes and aryl halides, respectively.…”

Rhodium-Catalyzed Decarbonylative Suzuki-Miyaura Cross-Coupling via in-Situ Generation of Acyl Fluorides from Carboxylic Acids

“…1 H NMR (400 MHz, CDCl 3 ) δ: 7.80 (dd,J＝10.7,7.6 Hz,2H),7.55 (d,J＝7.0 Hz,2H),7.50～7.44 (m,4H),7.40～7.36 (m,2H),7.32～7.27 (m,2H), 3.95 (s, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ: 143.2, 142.1, 141.5, 141.1, 140.9, 139.1, 128.5, 128.5, 127.4, 127.3, 127.2, 126.8, 126.7, 124.8, 120.0, 118.9, 36.8. 3-Methoxy-1,1'-biphenyl (3g): [14] Colorless oil, 15.8 mg, 43% yield. 1 H NMR (400 MHz, CDCl 3 ) δ: 7.58 (d,J＝7.2 Hz,2H),7.43 (t,J＝7.6 Hz,2H),7.37～7.33 (m,2H),7.18…”

Study on the Synthesis of Oxyresveratrol Catalyzed by Palladium

“…钯催化的 Heck 反应 [9,10] 和脱羧反应 [11,12] 在有机合成 中得到了广泛的应用. 由于烯烃存在难以合成、纯化困 难且容易聚合等问题 [13] , 所以原位合成烯烃并运用于 Heck 反应的方法也得到了广泛的研究和应用 [14] .…”

“…由于烯烃存在难以合成、纯化困 难且容易聚合等问题 [13] , 所以原位合成烯烃并运用于 Heck 反应的方法也得到了广泛的研究和应用 [14] . [11,12] . 3,5-二羟基碘苯在钯催化剂的作 用下生成中间体 I3, I3 与中间体 1 发生第二次 Heck 反 应: 氧化加成生成中间体 I4, 然后还原消除得目标产物 氧化芪三酚, 同时钯催化剂得以循环.…”