Computational Study on the Hetero-Diels-Alder Reactions between Phosphonodithioformate and Butadienes

被引：0

作者：

王岩 ^{[1
]}

曾小兰 ^{[1
]}

申赛军 ^{[2
]}

机构：

[1] College of Chemistry and Chemical Engineering, Xinyang Normal University

[2] Yangtang Middle School, Yangqiao Town, Shaodong

来源：

Chinese Journal of Structural Chemistry | 2008年 / 05期

关键词：

phosphonodithioformate; butadiene; hetero-Diels-Alder reaction; reaction mechanism; density functional theory;

D O I：

10.14102/j.cnki.0254-5861.2008.05.006

中图分类号：

O621.2 [有机化合物性质];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism, catalytic effect and substituent effect of the hetero-Diels-Alder reactions between phosphonodithioformate and butadienes have been investigated theoretically using density functional theory at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C and opposite result is found in other reactions. The BF3 catalyst and trimethylsilyloxy group may lower the activation barriers by changing the energies of FMOs for reactant molecules. With the BF3-catalyzed reactions, the complete regioselectivity observed experimentally has well been reproduced by theoretical calculation and these results originate probably from blue-shifting C-H···F hydrogen bond interaction in some transition states.

引用

页码：513 / 518

页数：6