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DFT Study on the Structure and Racemization Mechanism of 1,1'-Binaphthalene-8,8'-diol
Liang-guo Da1,2, Tong-tong Lu1, Mei Xiang,1, Tian-jing He1, Dong-ming Chen*1
1.Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China;2.Department of Chemical Biology, Huainan Normal University, Huainan 232001, China
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
附件
DFT Study on the Structure and Racemization Mechanism of 1,1'-Binaphthalene-8,8'-diol
笪良国1,2, 卢同同1, 向梅1, 何天敬1, 陈东明*1
1.中国科学技术大学化学物理系,合肥230026;2.淮南师范学院生物化学系,淮南232001
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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