反式二氯((4-氟苯基)-甲烷胺)钯(II)的合成及分子结构

Caleb D. Martin, F. Appoh, C. Vogels, A. Decken, S. Westcott
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引用次数: 0

摘要

利用钯配合物催化有机硼化合物与芳基卤化物或乙烯基卤化物的偶联已成为有机合成中应用最广泛的工具之一。Suzuki-Miyaura反应的范围和效用已经成为几篇优秀评论的主题在这种交叉偶联过程中使用硼酸是特别有利的,因为这些化合物相对无毒且热、空气和湿度稳定自从这种反应被发现以来,已经取得了许多进展。例如,使用芳基氯化物作为底物以及在低温和低催化剂负载下进行反应的能力大大增加了Suzuki-Miyaura交叉偶联反应的通用性。催化剂的发展也在改善该反应中发挥了重要作用,因为用于催化该转化的传统钯配合物含有气敏膦配体。近年来,大量的研究也集中在设计可用于在替代溶剂中进行该反应的新催化剂上本文报道了一种含氟苄胺钯配合物的合成及其分子结构,该配合物有望用于Suzuki-Miyaura交叉偶联反应。将PdCl2悬浮液(150 mg, 0.85 mmol)置于MeOH (15 mL)中,在室温下用NaCl (100 mg, 1.71 mmol)处理,搅拌1 h。在反应混合物中滴入2 mL的4氟苄胺(212 mg, 1.69 mmol)溶液,搅拌1 h,形成黄色沉淀物。通过吸力过滤收集固体,用甲醇(5ml)和己烷(10ml)洗涤,得到标题化合物。由DMSO在室温下重结晶得到结晶。收率:290 mg (80%);m.p = 495 - 497 K(分解)。NMR光谱数据(在DMSO-d6中):1H d值:7.50 (br m, 4H, Ar), 7.14 (br m, 4H, Ar), 3.97 (br s, 4H, CH2), 3.58 (br s, 4H, NH2);13C{1H} d: 162.0 (d, JC-F = 240 Hz, CF), 135.1, 131.3 (d, JC-F = 8 Hz, Ar), 115.4 (d, JC-F = 21 Hz, Ar), 47.4 (CH2);19F{1H} d: -115.3。FT-IR (Nujol): 3257, x射线结构分析在线
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Synthesis and Molecular Structure of trans-Dichlorodi((4-fluorophenyl)-methanamine)palladium(II)
The use of palladium complexes to catalyze the coupling of organoboron compounds with aryl or vinyl halides has become one of the most widely used tools in organic synthesis. The scope and utility of the Suzuki–Miyaura reaction has been the subject of several excellent reviews.1 The use of boronic acids in this cross coupling process is especially advantageous as these compounds are relatively nontoxic and thermally, airand moisture-stable.2 Numerous advances have been made to this reaction since its discovery. For instance, the use of aryl chlorides as substrates and the ability to conduct the reaction at low temperature and at low catalyst loading have greatly increased the versatility of the Suzuki–Miyaura cross coupling reaction. Catalyst development has also played a significant role in improving this reaction as traditional palladium complexes used to catalyze this transformation contain airsensitive phosphine ligands. In recent years, a considerable amount of research has also focused on designing new catalysts that can be used to carry out this reaction in alternative solvents.3 We report here on the synthesis and molecular structure of a palladium complex containing fluorinated benzylamines for its potential use in the Suzuki–Miyaura cross-coupling reaction. A suspension of PdCl2 (150 mg, 0.85 mmol) in MeOH (15 mL) was treated with NaCl (100 mg, 1.71 mmol) at RT and stirred for 1 h. A MeOH (2 mL) solution of 4fluorobenzylamine (212 mg, 1.69 mmol) was added dropwise to the reaction mixture and stirred for 1 h resulting in the formation of a yellow precipitate. The solid was collected by suction filtration and washed with MeOH (5 mL) and hexane (10 mL) to afford the title compound. Crystals were obtained by recrystallization from DMSO at RT. Yield: 290 mg (80%); m.p. = 495 – 497 K (decomposition). Spectroscopic NMR data (in DMSO-d6): 1H d: 7.50 (br m, 4H, Ar), 7.14 (br m, 4H, Ar), 3.97 (br s, 4H, CH2), 3.58 (br s, 4H, NH2); 13C{1H} d: 162.0 (d, JC-F = 240 Hz, CF), 135.1, 131.3 (d, JC-F = 8 Hz, Ar), 115.4 (d, JC-F = 21 Hz, Ar), 47.4 (CH2); 19F{1H} d: –115.3. FT-IR (Nujol): 3257, X-ray Structure Analysis Online
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