Metal-catalyzed nucleophilic carbon-heteroatom (C-X) bond formation: the role of M-X intermediates

Glueck DS

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Metal-catalyzed nucleophilic carbon-heteroatom (C-X) bond formation: the role of M-X intermediates

机译：金属催化的亲核碳杂原子（C-X）键形成：M-X中间体的作用

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Many important reactions that lead to carbon-heteroatom bond formation involve attack of anionic heteroatom nucleophiles, such as hydroxides, alkoxides, amides, thiolates and phosphides, at carbon. Related catalytic transformations are mediated by late transition metal complexes of these groups, which remain nucleophilic on metal coordination as a result of repulsive filled-filled interactions between the heteroatom lone pairs and metal d-orbitals and/or of polarization of the bonds M delta+-X delta-. This Perspective presents examples of catalytic nucleophilic C-X bond formation in both biological and synthetic systems and describes how changes in the metal, ancillary ligands and X groups may be used to tune nucleophilic reactivity.

机译：导致碳-杂原子键形成的许多重要反应涉及碳上阴离子杂原子亲核试剂的攻击，例如氢氧化物，醇盐，酰胺，硫醇盐和磷化物。这些基团的后期过渡金属络合物介导了相关的催化转化，这些金属络合物由于杂原子孤对与金属d轨道之间的排斥性填充填充相互作用和/或键M delta +-的极化而在金属配位上保持亲核性。 X delta-。本《观点》提供了在生物和合成系统中催化亲核C-X键形成的实例，并描述了金属，辅助配体和X基团的变化如何用于调节亲核反应性。

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《Dalton transactions: An international journal of inorganic chemistry》 |2008年第39期|共11页
作者
Glueck DS;
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正文语种 eng
中图分类无机化学;
关键词
P-STEREOGENIC PHOSPHINES; PARENT AMIDORUTHENIUM COMPLEX; O REDUCTIVE ELIMINATION; THIOLATE COMPLEXES; H BONDS; PROTEIN FARNESYLTRANSFERASE; ASYMMETRIC ALKYLATION; ELECTRONIC-STRUCTURE; KINETIC RESOLUTION; TERMINAL EPOXIDES;

机译：对-立体异构体;父AM络合物;O消除;硫醇盐络合物;H键;蛋白质法呢基转移酶;不对称烷基化;电子结构;动力学拆分;末端化合物;

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专利

1. Metal-catalyzed nucleophilic carbon-heteroatom (C-X) bond formation: the role of M-X intermediates [J] . Glueck DS Dalton transactions: An international journal of inorganic chemistry . 2008,第39期

机译：金属催化的亲核碳杂原子（C-X）键形成：M-X中间体的作用
2. Transition metal-catalyzed direct nucleophilic addition of C-H bonds to carbon-heteroatom double bonds [J] . Xi-Sha Zhang, Rang Chen, Zhang-Jie Shi Chemical science . 2014,第6期

机译：过渡金属催化的C-H键直接亲核加成至碳-杂原子双键
3. Transition Metal-Catalyzed Activation of Aliphatic C-X Bonds in Carbon-Carbon Bond Formation [J] . Tien-Yan Luh, Man-kit Leung, Ken-Tsung Wong Chemical Reviews . 2000,第8期

机译：碳-碳键形成中过渡金属催化的脂族C-X键活化
4. Carbon-Heteroatom Bond Cleavage Reactions of ortho-Substituted Phenols Assisted by Anchoring Bond to Ruthenium [C] . Hifomi Sato, Naoki Kurata, Nobuyuki Komine, Symposium on Organometallic Chemistry . 2003

机译：碳 - 杂原子键切割反应通过锚固至钌辅助的邻接酚辅助
5. Discovery and development of transition metal catalysts for carbon-carbon and carbon-heteroatom bond formations: Isolation and reactivity of catalytic intermediates. [D] . Stambuli, James Patrick. 2003

机译：用于碳-碳和碳-杂原子键形成的过渡金属催化剂的发现和开发：催化中间体的分离和反应。
6. The role of a 5alpha-hydroxylated intermediate in the formation of the 5 6-double bond in cholesterol biosynthesis. [O] . K Alexander, M Akhtar 1975

机译：5α-羟基化中间体在胆固醇生物合成中形成5、6-双键的作用。
7. Supramolecular Chemistry of Halogens: Complementary Features of Inorganic (M-X) and Organic (C-X) Halogens Applied to M-XX-C Halogen Bond Formation [O] . -1

机译：卤素的超分子化学：无机（M-X）的互补特征和施加到M-XX-C卤素键形成的有机（C-X）卤素

Metal-catalyzed nucleophilic carbon-heteroatom (C-X) bond formation: the role of M-X intermediates

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