Periselectivity and ambimodal transition states in cycloadditions of tetrachloro-o-benzoquinone with 6,6-dimethylfulvene

被引：0
作者：
Su, Ruirui [1 ]
He, Xue [1 ]
Houk, K. N. [2 ]
Lu, Qianqian [1 ,3 ]
Liu, Fang [1 ,2 ,3 ]
机构：
[1] Nanjing Agr Univ, Coll Sci, Nanjing, Peoples R China
[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA USA
[3] Nanjing Agr Univ, Coll Sci, Nanjing 210095, Peoples R China
来源：
JOURNAL OF COMPUTATIONAL CHEMISTRY | 2024年 / 45卷 / 11期
基金：
中国国家自然科学基金;
关键词：
6,6-dimethylfulvene; ambimodal transition states; distortion/interaction-activation strain (D/I-AS); orbital interaction; periselectivity; tetrachloro-o-benzoquinone; ACTIVATION STRAIN MODEL; 1,3-DIPOLAR CYCLOADDITIONS; DENSITY FUNCTIONALS; HARTREE-FOCK; ENERGIES; DISTORTION/INTERACTION; ORIGINS; MECHANISMS; QUINONES; FULVENES;
D O I：
10.1002/jcc.27264
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The reaction mechanism of cycloadditions of tetrachloro-o-benzoquinone with 6,6-dimethylfulvene were systematically investigated with density functional theory calculations. It was found that conditional primary interactions stabilize the ambimodal transition states in the endo pathways. Ambimodal transition states lead to [6 + 4]/[4 + 2] adducts or [4 + 2]/[2 + 4] adducts, which interconvert through 3,3-sigmatropic shift reactions. The substituent effects on periselectivity were also investigated.
引用
收藏
页码：752 / 760
页数：9
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