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题名: Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study
作者: Wang, Yi1;  Cai, Pei-Jun1;  Yu, Zhi-Xiang1
刊名: JOURNAL OF ORGANIC CHEMISTRY
发表日期: 2017-05-05
DOI: 10.1021/acs.joc.7b00194
卷: 82, 页:4604-4612
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Organic
研究领域[WOS]: Chemistry
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.
关键词[WOS]: 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
语种: 英语
WOS记录号: WOS:000401044700009
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/152297
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Peking Univ, BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China

Recommended Citation:
Wang, Yi,Cai, Pei-Jun,Yu, Zhi-Xiang. Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study[J]. JOURNAL OF ORGANIC CHEMISTRY,2017,82:4604-4612.
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