镍介导的芳基醚 C-O 键的氢解反应：氢的来源是什么？
Nickel-mediated hydrogenolysis of C-O bonds of aryl ethers: what is the source of the hydrogen?
机构信息
Department of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
出版信息
J Am Chem Soc. 2012 Mar 28;134(12):5480-3. doi: 10.1021/ja300326t. Epub 2012 Mar 13.
Abstract
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 H(2).
摘要
采用（二膦基）芳基甲基醚对镍催化芳基醚氢解的机理进行了研究。分离出了含有芳基-O 键相邻镍-芳烃相互作用的 Ni(0)配合物。加热导致芳基-O 键活化，并生成镍芳基甲氧基配合物。该物种的形式β-H 消除生成镍芳基氢化物，该氢化物在甲醛存在下可进行还原消除，生成 Ni(0)的一氧化碳加合物。所报道的配合物描绘了镍催化芳基醚氢解的合理机理。使用同位素标记的底物对先前报道的催化体系的研究与所提出的计量体系的机理一致，涉及镍烷氧基的β-H 消除，而不是 H(2)对 Ni-O 键的断裂。
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Angew Chem Int Ed Engl. 2011 Aug 8;50(33):7529-32. doi: 10.1002/anie.201102797. Epub 2011 Jun 27.
2
Kinetic isotope effects in the study of organometallic reaction mechanisms.有机金属反应机理研究中的动力学同位素效应
Chem Rev. 2011 Aug 10;111(8):4857-963. doi: 10.1021/cr100436k. Epub 2011 May 5.
3
Selective, nickel-catalyzed hydrogenolysis of aryl ethers.选择性镍催化芳基醚的氢解反应。
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4
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J Am Chem Soc. 2011 Apr 27;133(16):6352-63. doi: 10.1021/ja200398c. Epub 2011 Apr 1.
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Nickel hydrides supported by a non-innocent diphosphine arene pincer: mechanistic studies of nickel-arene H-migration and partial arene hydrogenation.由非亲核二膦芳烃钳形配体支撑的镍氢化物：镍-芳烃 H-迁移和部分芳烃氢化的机理研究。
J Am Chem Soc. 2011 Mar 23;133(11):3828-31. doi: 10.1021/ja200368y. Epub 2011 Feb 23.
6
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Chem Commun (Camb). 2011 Mar 14;47(10):2946-8. doi: 10.1039/c0cc05169a. Epub 2011 Jan 24.
7
Nickel-catalyzed cross-couplings involving carbon-oxygen bonds.镍催化的涉及碳-氧键的交叉偶联反应。
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8
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J Am Chem Soc. 2010 May 12;132(18):6296-7. doi: 10.1021/ja101699a.
10
The catalytic valorization of lignin for the production of renewable chemicals.木质素催化转化制备可再生化学品
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