Direct observation of the oxidative addition of the aryl carbon-oxygen bond to a ruthenium complex and consideration of the relative reactivity between aryl carbon-oxygen and aryl carbon-hydrogen bonds
Direct observation of the oxidative addition of the aryl carbon-oxygen bond to a ruthenium complex and consideration of the relative reactivity between aryl carbon-oxygen and aryl carbon-hydrogen bonds
复制标题
DOI：
10.1021/ja067612p
复制
发表时间：
2006-12-27
影响因子：
15
通讯作者：
Kakiuchi, Fumitoshi
中科院分区：
文献类型：
--
作者：
Ueno, Satoshi;Mizushima, Eiichiro;Kakiuchi, Fumitoshi
当RuH 2（CO）（PPh 3）3与2，2-二甲基-1-（2-对甲苯基苯基）丙-1-酮（2）反应时，以76%的产率得到钌芳氧基配合物3。配合物的结构由~ 1H、~（31）P NMR和X射线衍射数据确定。配合物3对2与苯硼酸酯4的偶联反应具有催化活性。对Ru（CO）（PPh 3）3与邻芳氧基特戊酮反应的~ 1H和~（31）P NMR研究表明，C−H键的断裂是一个动力学上有利的过程，而C−O键的断裂是一个热力学上有利的过程. 2 '-甲氧基苯乙酮与乙烯基硅烷和有机硼酸酯的反应导致化学选择性的C-C键形成。
When RuH2(CO)(PPh3)3was reacted with 2,2-dimethyl-1-(2-p-tolylphenyl)propan-1-one (2), the ruthenium−aryloxy complex3was obtained in 76% yield. The structure of this complex was determined from1H and31P NMR and X-ray data. Complex3showed the catalytic activity for the coupling of2with the phenylboronate4. The1H and31P NMR studies of the reaction of Ru(CO)(PPh3)3witho-aryloxy pivalophenone revealed that the C−H bond cleavage is a kinetically favorable process but the C−O bond cleavage is a thermodynamic one. The reaction of 2‘-methoxyacetophenone with vinylsilane and organoboronate resulted in chemoselective C−C bond formation.