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DFT Study on the Structure and Racemization Mechanism of 1,1'-Binaphthalene-8,8'-diol
Liang-guo Da,Tong-tong Lu,Mei Xiang,,Tian-jing He,Dong-ming Chen*
Author NameAffiliationE-mail
Liang-guo Da Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China; Department of Chemical Biology, Huainan Normal University, Huainan 232001, China  
Tong-tong Lu Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Mei Xiang, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Tian-jing He Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Dong-ming Chen* Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China dmchen@ustc.edu.cn 
Abstract:
Density functional theory (DFT) was applied to study the ground state geometries and isomerization processes of 1,1'-binaphthalene-8,8'-diol. Three isomers, denoted as ISO1, ISO2, and ISO3, were found, distinguished by different orientations of the OH groups, and each OH-orientational isomer has R- and S- enantiomer. The conformational stabilities of these isomers were investigated by tracking the energy change with respect to the ring-to-ring torsion. The inter-conversions between the three OH-orientational S-isomers were found to have quite low barriers owing to the nearly free rotation of OH groups around the O-C single bonds. The S-R enantiomerization of ISO1 and ISO2 can take place through the ring-ring torsion around the C1-C10 single bond, either in the anti-rotation manner or in the syn-rotation manner. The barriers of the anti routes are lower than those of the corresponding syn routes by 87.95 and 75.04 kJ/mol. For the S-R enantiomerization of ISO3, only the anti route was found. The barriers for the anti route enantiomerizations of ISO1, ISO2, and ISO3 are 119.61, 120.43, and 121.59 kJ/mol, respectively. A parallel reaction mechanism via three anti enantiomerization routes was proposed for the racemization of 1,1'-binaphthalene-8,8'-diol.
Key words:  Density functional theory (DFT), 1,1'-Binaphthalene-8,8'-diol, Racemization
FundProject:国家自然科学基金
DFT Study on the Structure and Racemization Mechanism of 1,1'-Binaphthalene-8,8'-diol
笪良国,卢同同,向梅,何天敬,陈东明*
摘要:
用密度泛函理论研究了1,1'-联萘-8,8'-二酚的基态几何构型和异构化过程.由于OH基取向不同,该分子可以形成三种异构体(ISO1、ISO2和ISO3), 每种OH取向异构体分别有R-和S-对映异构体.研究了各异构体关于萘酚环旋转变形的构像稳定性.由于O-C键单键性质,三种OH取向异构体间的互变反应的能垒较低,表明它们可以很快达到平衡.对于ISO1和ISO2,S-R对映异构反应可以通过绕C1-C10键的反式或顺式旋转途径进行,其中反式途径比顺式途径的能垒分别低87.95 kJ/mol(ISO1)和75.04 kJ/mol(ISO2).对于ISO3,S-R对映异构反应只能通过反式途径进行.三种OH取向异构体的反式途径对映异构反应的能垒分别为119.61、120.43和121.59 kJ/mol.计算结果认为,1,1'-联萘-8,8'-二酚的消旋机理被归结为三种OH取向异构体的反式途径对映异构反应的平行进行.
关键词:  密度泛函理论,1,1'-联萘-8,8'-二酚,消旋反应
DOI:10.1088/1674-0068/21/04/367-375
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