Theoretical studies of 5-exo selective intramolecular cyclization of o-alkynylbenzoic acid catalyzed by organic base
Theoretical studies of 5-exo selective intramolecular cyclization of o-alkynylbenzoic acid catalyzed by organic base
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DOI：
10.3987/com-07-s(w)73
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发表时间：
2007-12
期刊：
影响因子：
0.6
通讯作者：
M. Terada;C. Kanazawa;M. Yamanaka
中科院分区：
文献类型：
--
作者：
M. Terada;C. Kanazawa;M. Yamanaka
对有机碱催化邻炔基苯甲酸的5-外环化反应进行了理论研究。基于5-exo和6-endo过渡态的混合密度泛函理论(BHandHLYP)计算表明，参与过渡态的酸性碎片显著降低了反应的活化能。此外，通过对过渡态和反应物的优化结构的自然布居分析，对5-exo环化模式的偏好进行了合理化。
Theoretical studies of the organic base-catalyzed 5-exo intramolecular cyclization of o-alkynylbenzoic acid were documented. The acidic fragment participating in the transition states was shown to reduce the activation energy significantly on the basis of hybrid DFT (BHandHLYP) calculation of 5-exo and 6-endo transition states. Furthermore, preference for the 5-exo cyclization mode was rationalized by natural population analysis of optimized structures of the transition states and the reactants.