Ruthenium-catalyzed [2+2] cycloadditions between substituted alkynes and norbornadiene: a theoretical study

被引:16
作者
Liu, Peng [1 ]
Tam, William [1 ]
Goddard, John D. [1 ]
机构
[1] Univ Guelph, Dept Chem, Guelph, ON N1G 2W1, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
D O I
10.1016/j.tet.2007.05.030
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Theoretical predictions have been made using density functional theory for the reaction paths of a series of substituted alkynes undergoing a ruthenium-catalyzed cycloaddition with norbornadiene. Substituents on the alkynes have been varied in order to probe electronic and steric effects and the role of an intramolecular hydrogen bond. Strong electron-withdrawing groups activate the alkyne and decrease the reaction barrier leading to an increased rate. Bulkier substituents are predicted to lead to higher barriers and slower rates. The hydroxyl group on the alkyne hydrogen bonds to the chlorine stabilizes the transition state and increases the reaction rate. Generally good agreement is found with the trends in recently reported experimental relative rates of reaction of substituted alkynes with norbornadiene. (C) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:7659 / 7666
页数:8
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