Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active‐Metal‐Template Synthesis of [2]Rotaxanes,Angewandte Chemie International Edition

当前位置： X-MOL 学术 › Angew. Chem. Int. Ed. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active‐Metal‐Template Synthesis of [2]Rotaxanes
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-06-20 , DOI: 10.1002/anie.201803934
Arthur F. P. Alcântara _{1,

2} , Liniquer A. Fontana ₁ , Vitor H. Rigolin ₁ , Yuri F. S. Andrade ₁ , Marcos A. Ribeiro ₁ , Wdeson P. Barros ₁ , Catia Ornelas ₁ , Jackson D. Megiatto ₁

Affiliation

A Co^II/porphyrinate‐based macrocycle in the presence of a 3,5‐diphenylpyridine axial ligand functions as an endotopic ligand to direct the assembly of [2]rotaxanes from diazo and styrene half‐threads, by radical‐carbene‐transfer reactions, in excellent 95 % yield. The method reported herein applies the active‐metal‐template strategy to include radical‐type activation of ligands by the metal‐template ion during the organometallic process which ultimately yields the mechanical bond. A careful quantitative analysis of the product distribution afforded from the rotaxane self‐assembly reaction shows that the Co^II/porphyrinate subunit is still active after formation of the mechanical bond and, upon coordination of an additional diazo half‐thread derivative, promotes a novel intercomponent C−H insertion reaction to yield a new rotaxane‐like species. This unexpected intercomponent C−H insertion illustrates the distinct reactivity brought to the Co^II/porphyrinate catalyst by the mechanical bond.

中文翻译：

钴（II）/卟啉酸酯促进的自由基碳转移反应进行烯烃环丙烷化：[2]轮烷的活性金属模板合成

在3,5-二苯基吡啶轴向配体存在的情况下，基于Co ^II /卟啉的大环作为内位配体，通过自由基-卡宾-转移反应，指导重氮和苯乙烯半螺纹中[2]轮烷的组装，产率高达95％。本文报道的方法采用了活性金属模板策略，包括在有机金属过程中通过金属模板离子对配体进行自由基型活化。对轮烷自组装反应提供的产物分布进行仔细的定量分析表明，Co ^II/卟啉亚基在形成机械键后仍然有效，并且在与其他重氮半螺纹衍生物配位后，会促进新型的C-H互插入反应，从而产生新的轮烷样物质。这种出乎意料的C–H中间插入说明了通过机械键带给Co ^II /卟啉酸酯催化剂的独特反应性。

更新日期：2018-06-20

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11