Lewis acid-catalyzed [4+3] cycloaddition of 2-(trimethyl silyloxy)acrolein with furan. Insight on the nature of the mechanism from a DFT analysis
Lewis acid-catalyzed [4+3] cycloaddition of 2-(trimethyl silyloxy)acrolein with furan. Insight on the nature of the mechanism from a DFT analysis
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DOI：
10.1021/ol035652h
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发表时间：
2003-10-30
期刊：
影响因子：
5.2
通讯作者：
Domingo, LR
中科院分区：
文献类型：
--
作者：
Sáez, JA;Arnó, M;Domingo, LR
[GRAPHIC]在B3 LYP/6- 31 G * 水平上研究了刘易斯酸催化的2-（三甲基硅氧基）丙烯醛1与呋喃2的[4 + 3]环加成反应机理.该反应是一个三步过程，其通过2对1的β-共轭位置的亲核攻击来初始化，得到两性离子中间体IN 1。七元环形成的关键步骤是呋喃残基对该中间体中亲电活性羰基碳的亲电攻击。
[GRAPHIC]The mechanism for the Lewis acid-catalyzed [4 + 3] cycloaddition of 2-(trimethylsilyloxy)acrolein 1 with furan 2 has been studied at the B3LYP/6-31G* level. This reaction is a three-step process that is initialized by the nucleophilic attack of 2 to the beta-conjugated position of 1 to give a zwitterionic intermediate IN1. The key step on the formation of the seven-membered ring is the electrophilic attack of the furan residue to the electrophilically activated carbonyl carbon at this intermediate.