Sigmatropic proton shifts: a quantum chemical study | |
Wang, Yi; Yu, Zhi-Xiang | |
刊名 | ORGANIC & BIOMOLECULAR CHEMISTRY |
2017-09-21 | |
卷号 | 15期号:35页码:7439-7446 |
英文摘要 | A quantum chemical study of [1, j] sigmatropic proton shifts in polyenyl anions and related conjugated systems has been performed. We found that the Woodward-Hoffmann rules can be applied to understand the stereochemical outcome of these sigmatropic rearrangements, showing that [1, j] sigmatropic proton shift occurs antarafacially when j = 4n + 2, while suprafacial proton shift is symmetry-allowed when j = 4n. The activation barriers for [1, j] proton shifts in polyenyl anions CjHj+3- are 48.2 (j = 2), 32.8 (j = 4), 21.0 (j = 6), 40.5 (j = 8), and 49.1 (j = 10) kcal mol(-1), respectively. This trend can be explained by the trade-off between stereoelectronic requirement and ring strain in the proton shift transition structure. Among these reactions, only the [1,6] proton shift with the lowest activation barrier can occur intra-molecularly under mild reaction conditions. The others are unlikely to take place in a direct manner. Consequently, proton shuttles are generally required to facilitate these sigmatropic proton shifts through a protonation/deprotonation mechanism. |
WOS标题词 | Science & Technology ; Physical Sciences |
类目[WOS] | Chemistry, Organic |
研究领域[WOS] | Chemistry |
关键词[WOS] | REIMER-TIEMANN REACTION ; HETEROATOM DIRECTED PHOTOARYLATION ; GAUSSIAN-BASIS SETS ; N-ARYL ENAMINES ; CORRELATED MOLECULAR CALCULATIONS ; CATALYZED 3+2 CYCLOADDITION ; ENOL ETHER FORMATION ; ALPHA-DIAZO KETONES ; O-H INSERTION ; TRANSITION STRUCTURES |
收录类别 | SCI |
语种 | 英语 |
WOS记录号 | WOS:000411462600029 |
内容类型 | 期刊论文 |
源URL | [http://cas-ir.dicp.ac.cn/handle/321008/150190] |
专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
作者单位 | Peking Univ, BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China |
推荐引用方式 GB/T 7714 | Wang, Yi,Yu, Zhi-Xiang. Sigmatropic proton shifts: a quantum chemical study[J]. ORGANIC & BIOMOLECULAR CHEMISTRY,2017,15(35):7439-7446. |
APA | Wang, Yi,&Yu, Zhi-Xiang.(2017).Sigmatropic proton shifts: a quantum chemical study.ORGANIC & BIOMOLECULAR CHEMISTRY,15(35),7439-7446. |
MLA | Wang, Yi,et al."Sigmatropic proton shifts: a quantum chemical study".ORGANIC & BIOMOLECULAR CHEMISTRY 15.35(2017):7439-7446. |
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