Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Alkynes through C-H Activation

被引：26

作者：

Kawaguchi, Yasuaki ^{[1
]}

Yasuda, Shigeo ^{[1
]}

Kaneko, Akira ^{[1
]}

Oura, Yuki ^{[1
]}

Mukai, Chisato ^{[1
]}

机构：

[1] Kanazawa Univ, Grad Sch Med Sci, Div Pharmaceut Sci, Kanazawa, Ishikawa 9201192, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 29期

关键词：

alkynes; allenes; C-H activation; cycloisomerization; rhodium; CATALYZED 5+2 CYCLOADDITIONS; BOND ACTIVATION; VINYLCYCLOPROPANES; ALLENYNES; 1ST; SELECTIVITY; CYCLIZATION; COMPLEXES; CHIRALITY; ALKENES;

D O I：

10.1002/anie.201403990

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The efficient Rh-I-catalyzed cycloisomerization of benzylallene-alkynes produced the tricyclo[9.4.0.0(3,8)]pentadecapentaene skeleton through a C-sp2-H bond activation in good yields. A plausible reaction mechanism proceeds via oxidative addition of the acetylenic C-H bond to Rh-I, an enetype cyclization to the vinylidenecarbene-Rh-I intermediate, and an electrophilic aromatic substitution with the vinylidenecarbene species. It was proposed based on deuteration and competition experiments.

引用

页码：7608 / 7612

页数：5

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