Carbanion Translocations via Intramolecular Proton Transfers: A Quantum   Chemical Study

doi:10.1021/acs.joc.7b00194

CORC > 北京大学 > 化学与分子工程学院

	Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study
	Wang, Yi ; Cai, Pei-Jun ; Yu, Zhi-Xiang
刊名	JOURNAL OF ORGANIC CHEMISTRY
	2017
关键词	GAUSSIAN-BASIS SETS TRANSITION-STATE METHOD CORRELATED MOLECULAR CALCULATIONS CATALYZED 3+2 CYCLOADDITION COUPLED ELECTRON-TRANSFER ALPHA-AMINO NITRILES NATURAL ORBITALS GAS-PHASE THEORETICAL-ANALYSIS TAXADIENE SYNTHASE
DOI	10.1021/acs.joc.7b00194
英文摘要	Intramolecular proton transfers are important processes in chemical reactions and biological transformations. In particular, the translocation of reactive carbanion centers can be achieved through 1,n-proton transfer in either a direct or an assisted manner (via the protonation/deprotonation mechanism). Despite some mechanistic investigations on proton transfers within zwitterionic species, no guiding principles have been summarized for carbanion-induced intramolecular proton transfers. Herein, we report our quantum chemical study on the carbanion translocations via intramolecular proton transfers. Our calculations indicated that the reaction barriers generally decrease with longer tether lengths and more ?-withdrawing substituents. The physical bases behind these effects were revealed according to the charge and bond energy decomposition analysis, showing that the destabilizing closed-shell Pauli repulsions play important roles in determining the relative ease of intramolecular proton transfers. We also found that the thermodynamic driving force may affect the regiochemistry. This study may help chemists to understand whether a carbanion translocation occurs via an intramolecular proton transfer or with the assistance of proton shuttles, such as water and alcohols.; National Natural Science Foundation of China [21232001]; SCI(E); ARTICLE; 9; 4604-4612; 82
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/473480]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, Yi,Cai, Pei-Jun,Yu, Zhi-Xiang. Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study[J]. JOURNAL OF ORGANIC CHEMISTRY,2017.
APA	Wang, Yi,Cai, Pei-Jun,&Yu, Zhi-Xiang.(2017).Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study.JOURNAL OF ORGANIC CHEMISTRY.
MLA	Wang, Yi,et al."Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study".JOURNAL OF ORGANIC CHEMISTRY (2017).