Intramolecular Hydrogen Bonding in α-Epoxy Alcohols: A Conformational Analysis of 1,2-Dialkyl-2,3-epoxycyclopentanol Diastereomers
Intramolecular Hydrogen Bonding in α-Epoxy Alcohols: A Conformational Analysis of 1,2-Dialkyl-2,3-epoxycyclopentanol Diastereomers
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DOI：
10.1246/cl.170932
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发表时间：
2018-01-01
影响因子：
1.6
通讯作者：
Tschumper, Gregory S.
中科院分区：
文献类型：
--
作者：
Abdo, Yasmeen A.;Weeks, Justin W.;Tschumper, Gregory S.
采用M06-2X/cc-pVTZ方法对11种1，2-二取代-2，3-环氧环戊醇非对映异构体进行了几何构型优化，探讨了α-环氧醇半频哪醇重排反应的机理.活性顺式非对映异构体的电子能量平均比反式非对映异构体低0.9 kcal mol（-1）。分子内氢键使顺式底物能量平均稳定3.4千卡摩尔。
Geometry optimizations for 11 1,2-disubstituted-2,3-epoxy-cyclopentanol diastereomers were studied using the M06-2X/cc-pVTZ method and basis set to probe mechanistic details in the alpha-epoxy alcohol semipinacol rearrangement reaction. Electronic energies of active cis diastereomers are on average 0.9 kcal mol(-1) lower than trans diastereomers. Intramolecular hydrogen bonding stabilizes the cis substrate energy by 3.4 kcal mol(-1), on average.