中国科学院大连化学物理研究所机构知识库
Advanced  
DICP OpenIR  > 中国科学院大连化学物理研究所  > 期刊论文
题名: Sigmatropic proton shifts: a quantum chemical study
作者: Wang, Yi1;  Yu, Zhi-Xiang1
刊名: ORGANIC & BIOMOLECULAR CHEMISTRY
发表日期: 2017-09-21
DOI: 10.1039/c7ob01628j
卷: 15, 期:35, 页:7439-7446
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: 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.
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
语种: 英语
WOS记录号: WOS:000411462600029
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/150190
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

Files in This Item:

There are no files associated with this item.


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,Yu, Zhi-Xiang. Sigmatropic proton shifts: a quantum chemical study[J]. ORGANIC & BIOMOLECULAR CHEMISTRY,2017,15(35):7439-7446.
Service
 Recommend this item
 Sava as my favorate item
 Show this item's statistics
 Export Endnote File
Google Scholar
 Similar articles in Google Scholar
 [Wang, Yi]'s Articles
 [Yu, Zhi-Xiang]'s Articles
CSDL cross search
 Similar articles in CSDL Cross Search
 [Wang, Yi]‘s Articles
 [Yu, Zhi-Xiang]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
  Add to CiteULike  Add to Connotea  Add to Del.icio.us  Add to Digg  Add to Reddit 
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace