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Sigmatropic proton shifts: a quantum chemical study
Wang, Yi; Yu, Zhi-Xiang
Source PublicationORGANIC & BIOMOLECULAR CHEMISTRY
2017-09-21
DOI10.1039/c7ob01628j
Volume15Issue:35Pages:7439-7446
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Organic
WOS Research AreaChemistry
WOS KeywordREIMER-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
AbstractA 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.
Language英语
WOS IDWOS:000411462600029
Citation statistics
Cited Times:6[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/150090
Collection中国科学院大连化学物理研究所
AffiliationPeking Univ, BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China
Recommended Citation
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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