Nickel-mediated hydrogenolysis of C-O bonds of aryl ethers: what is the source of the hydrogen?
Nickel-mediated hydrogenolysis of C-O bonds of aryl ethers: what is the source of the hydrogen?
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镍介导的芳基醚 C-O 键氢解：氢的来源是什么？
DOI：
10.1021/ja300326t
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发表时间：
2012-03-28
影响因子：
15
通讯作者：
Agapie, Theodor
中科院分区：
文献类型：
--
作者：
Kelley, Paul;Lin, Sibo;Edouard, Guy;Day, Michael W.;Agapie, Theodor
用（二膦）芳基甲基醚对镍催化的芳基醚氢解反应进行了机理研究。分离出一个含有镍-芳烃相互作用的镍（0）配合物，该配合物与芳基-O键相邻。加热导致芳基-O键活化并产生镍-芳基-甲醇盐复合物。从该物种中进行的形式β-H消除产生镍-芳基-氢化物，其可以在甲醛存在下进行还原消除以产生Ni（0）的一氧化碳加合物。报道的配合物映射出一个合理的机制，芳基醚氢解镍催化。使用同位素标记的底物的先前报道的催化体系的调查与化学计量体系中提出的机制一致，涉及从镍醇盐中消除β-H，而不是通过H2裂解Ni-O键。
Mechanistic studies of the hydrogenolysis of aryl ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni-arene interactions adjacent to the aryl-O bond was isolated. Heating led to aryl-O bond activation and generation of a nickel-aryl-methoxide complex. Formal β-H elimination from this species produced a nickel-aryl-hydride which can undergo reductive elimination in the presence of formaldehyde to generate a carbon monoxide adduct of Ni(0). The reported complexes map out a plausible mechanism of aryl ether hydrogenolysis catalyzed by nickel. Investigations of a previously reported catalytic system using isotopically labeled substrates are consistent with the mechanism proposed in the stoichiometric system, involving β-H elimination from a nickel alkoxide rather than cleavage of the Ni-O bond by H2.
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影响因子：
15
作者：
Quasdorf, Kyle W.;Antoft-Finch, Aurora;Liu, Peng;Silberstein, Amanda L.;Komaromi, Anna;Blackburn, Tom;Ramgren, Stephen D.;Houk, K. N.;Snieckus, Victor;Garg, Neil K.
通讯作者：
Garg, Neil K.
影响因子：
4.9
作者：
Cámpora, J;Conejo, MD;Passaglia, E
通讯作者：
Passaglia, E
影响因子：
15
作者：
Alvarez-Bercedo, Paula;Martin, Ruben
通讯作者：
Martin, Ruben
影响因子：
15
作者：
BRYNDZA, HE;CALABRESE, JC;BERCAW, JE
通讯作者：
BERCAW, JE
影响因子：
2.3
作者：
Issenhuth, Jean-Thomas;Notter, Francois-Paul;Bellemin-Laponnaz, Stephane
通讯作者：
Bellemin-Laponnaz, Stephane