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铼催化偶氮苯与醛通过可分离的环状铼(I)配合物进行的[4 + 1]环化反应。

Rhenium-Catalyzed [4 + 1] Annulation of Azobenzenes and Aldehydes via Isolable Cyclic Rhenium(I) Complexes.

作者信息

Geng Xiaoyu, Wang Congyang

机构信息

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

出版信息

Org Lett. 2015 May 15;17(10):2434-7. doi: 10.1021/acs.orglett.5b00938. Epub 2015 May 6.

Abstract

The first Re-catalyzed [4 + 1] annulation of azobenzenes with aldehydes was developed to furnish 2H-indazoles via isolable and characterized cyclic Re(I)-complexes. For the first time, the acetate-acceleration effect is showcased in Re-catalyzed C-H activation reactions. Remarkably, mechanistic studies revealed an irreversible aldehyde-insertion step, which is in sharp contrast to those of previous Rh- and Co-systems.

摘要

首次开发了偶氮苯与醛的再催化[4 + 1]环化反应,通过可分离和表征的环状铼(I)配合物制备2H-吲唑。首次在铼催化的C-H活化反应中展示了乙酸根加速效应。值得注意的是,机理研究揭示了一个不可逆的醛插入步骤,这与之前的铑和钴体系形成了鲜明对比。

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