Rhodium-Catalyzed Intramolecular [5+2] Cycloaddition of Inverted 3-Acyloxy-1,4-enyne and Alkyne: Experimental and Theoretical Studies

被引：14
|
作者：
Li, Xiaoxun [1 ]
Song, Wangze [1 ]
Ke, Xiaona [2 ]
Xu, Xiufang [2 ]
Liu, Peng [3 ]
Houk, K. N. [4 ]
Zhao, Xian-liang [1 ,5 ]
Tang, Weiping [1 ,6 ]
机构：
[1] Univ Wisconsin, Sch Pharm, 425 N Charter St, Madison, WI 53706 USA
[2] Nankai Univ, Dept Chem, Key Lab Adv Energy Mat Chem, Minist Educ, Tianjin 300071, Peoples R China
[3] Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA
[4] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[5] Zhejiang Univ Sci & Technol, Sch Biol & Chem Engn, Hangzhou 310023, Zhejiang, Peoples R China
[6] Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 21期
基金：
美国国家科学基金会; 中国国家自然科学基金;
关键词：
catalysis; cycloaddition; enynes; rhodium; seven-membered rings; DENSITY-FUNCTIONAL THEORY; DIELS-ALDER REACTION; 7-MEMBERED RINGS; NATURAL SESQUITERPENOIDS; PROPARGYLIC ESTERS; VINYL AZIRIDINES; ENE REACTIONS; VINYLCYCLOPROPANES; MECHANISM; SELECTIVITY;
D O I：
10.1002/chem.201601195
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
By switching the position of the alkene and alkyne, a new type of 3-acyloxy-1,4-enyne (ACE) five-carbon building block was developed for Rh-catalyzed intramolecular [5+2] cycloaddition. An electron-withdrawing acyl group on the alkyne termini of the ACE was essential for a regioselective 1,2-acyloxy migration. This new method provided bicyclic [5.3.0]decatrienes that are different from previous methods because of the positions of the alkenes and the acyloxy group. Multiple mechanistic pathways become possible for this new [5+2] cycloaddition and they are investigated by computational studies.
引用
收藏
页码：7079 / 7083
页数：5
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