Conformational and linkage isomerizations for dihapto-coordinated arenes and aromatic heterocycles: controlling the stereochemistry of ligand transformations

W. Dean Harman

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Conformational and linkage isomerizations for dihapto-coordinated arenes and aromatic heterocycles: controlling the stereochemistry of ligand transformations

机译：二配位芳烃和芳香杂环的构象和连接异构化：控制配体转化的立体化学

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Arenes and aromatic heterocycles have cyclic skeletons made up completely of unsaturated carbons. Through their dihapto coordination to a transition metal, controlled addition reactions can be accomplished with good stereocontrol, relative to the position of the metal. The metal can readily undergo inter- and intrafacial linkage isomerizations in these complexes. By controlling these processes using chiral auxiliaries on the arene, stereogenic metal centers, or solid-state induced control of kinetically unstable stereoisomers (SICKUS), enantio-enriched organic compounds can be realized from this methodology. This work outlines what is known about conformational and linkage isomerizations in dihapto-coordinated aromatic complexes, and demonstrates their relevance to organic synthesis.

机译：芳烃和芳香族杂环具有完全由不饱和碳组成的环状骨架。通过它们与过渡金属的二配位配位，相对于金属的位置，可以通过良好的立体控制完成受控的加成反应。在这些络合物中，金属很容易发生界面内和界面键异构化。通过使用芳烃上的手性助剂，立体金属中心或固态诱导的动力学不稳定立体异构体（SICKUS）的控制来控制这些过程，可以从该方法中实现对映体富集的有机化合物。这项工作概述了二配位的芳香族络合物中构象和连接异构化的已知信息，并证明了它们与有机合成的相关性。

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来源
《Coordination chemistry reviews》 |2004年第10期|p.853-866|共14页
作者
W. Dean Harman;
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作者单位

Department of Chemistry, University of Virginia, McCormick Road, Charlottesville, VA 22904-4319, USA;

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收录信息美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);
原文格式 PDF
正文语种 eng
中图分类无机化学;
关键词
isomerization; osmium; rhenium; tungsten; molybdenum; arene; dearomatization;

机译：异构化;ium;钨;钼;芳烃;脱芳香化;

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机译：I.多催化作用：在复杂的杂环化合物的合成中三氟甲磺酸铋（III）催化的亲核加成/加氢官能化反应的发展。羰基钯催化剂对芳烃和杂芳烃的CH-H芳基化反应：催化剂静止状态的鉴定以及新戊酸酯配体在稳定催化剂中的关键作用III。羰基钯催化剂催化杂芳烃的CH芳基化：膦配体对基础杂芳烃基质的重要性IV。杂芳烃与钯-羧酸酯的CH芳基化：碱性杂芳烃底物性能对直接芳基化的影响。
6. Arene Oxides as Intermediates in the Metabolism of Aromatic Substrates: Alkyl and Oxygen Migrations during Isomerization of Alkylated Arene Oxides [O] . Donald M. Jerina, Nikolaus Kaubisch, John W. Daly 1971

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7. Arene Oxides as Intermediates in the Metabolism of Aromatic Substrates: Alkyl and Oxygen Migrations during Isomerization of Alkylated Arene Oxides [O] . Jerina, Donald M., Kaubisch, Nikolaus, Daly, John W. 1971

机译：作为芳族底物代谢中间产物的芳烃氧化物：烷基化芳烃氧化物异构化过程中的烷基和氧迁移

Conformational and linkage isomerizations for dihapto-coordinated arenes and aromatic heterocycles: controlling the stereochemistry of ligand transformations

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