Catalysts for Suzuki-Miyaura coupling processes: Scope and studies of the effect of ligand structure
Catalysts for Suzuki-Miyaura coupling processes: Scope and studies of the effect of ligand structure
复制标题
DOI：
10.1021/ja042491j
复制
发表时间：
2005-04-06
影响因子：
15
通讯作者：
Buchwald, SL
中科院分区：
文献类型：
--
作者：
Barder, TE;Walker, SD;Buchwald, SL
芳基和杂芳基卤化物与芳基，杂芳基和乙烯基硼酸的铃木 - 米约龙偶联反应，使用2-（2'，6'-二甲氧基甲氧基）dicycloheclyhexylphasphiphine，sphos，sphos（1）。这种配体为这些过程赋予了前所未有的活性，允许在低催化剂水平下进行反应，以制备极具阻碍的双子体，并通常在室温下对芳基氯化物的反应进行。此外，提供了各种1（。）PD复合物的结构研究以及计算数据，有助于阐明1对铃木 - 米约拉拉耦合过程的功效。此外，提出了与2-（2'，4'，4'，6'三甲苯二苯基）二苯基膦（2）的反应的比较，这些反应在确定高体积和电子在高含量中的相对重要性是有益的。源自这种类型配体的催化剂的活性。此外，当芳基溴化物变得过于阻碍时，有趣的C-H键函数化 - 耦合序列会介入以高产量提供产物。
Suzuki-Miyaura coupling reactions of aryl and heteroaryl halides with aryl-, heteroaryl- and vinylboronic acids proceed in very good to excellent yield with the use of 2-(2 ',6 '-dimethoxybiphenyl)dicyclohexylphosphine, SPhos (1). This ligand confers unprecedented activity for these processes, allowing reactions to be performed at low catalyst levels, to prepare extremely hindered biaryls and to be carried out, in general, for reactions of aryl chlorides at room temperature. Additionally, structural studies of various 1(.)Pd complexes are presented along with computational data that help elucidate the efficacy that 1 imparts on Suzuki-Miyaura coupling processes. Moreover, a comparison of the reactions with 1 and with 2-(2 ',4 ',6 '-triisopropylbiphenyl)diphenylphosphine (2) is presented that is informative in determining the relative importance of ligand bulk and electron-donating ability in the high activity of catalysts derived from ligands of this type. Further, when the aryl bromide becomes too hindered, an interesting C-H bond functionalization-cross-coupling sequence intervenes to provide product in high yield.