理论研究金(Ⅰ)催化环化吲哚反应的机理:配阴离子对质子转移的影响
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- 英文论文题名：Theoretical study on mechanism of Au(Ⅰ)-catalyzed cyclization of indole:effects of anion ligands on the proton-transfer
- 论文作者：袁斌芳 ; 李明
- 英文论文作者：Binfang Yuan ; Ming Li ; Southwest University ; College of Chemistry and Chemical Engineering
- 年：2016
- 作者机构：西南大学化学化工学院;
- 论文关键词：DFT ; 质子转移 ; 理论探究 ; 配阴离子
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十九分会：化学中的量子与经典动力学
- 语种：中文
- 分类号：O621.25
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十九分会 ; 化学中的量子与经典动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：166k
- 原文格式：D
- 会议级别：全国
摘要
通过研究金(Ⅰ)催化环化吲哚反应~([1])的机理,探索配阴离子对质子转移的影响。计算结果表明配阴离子Cl~-,OTf~-和BF_4~-作为质子shuttle可以大大降低质子转移过程中的能垒。更为重要的是,我们的计算发现配阴离子的质子碱性强弱(Cl~->OTf~->BF_4~-)是导致阴离子协助质子转移能力差异性的根本原因。在配阴离子的质子化过程中,配阴离子对这一过程的催化能力趋势为Cl~->OTf~->BF_4~-(见图1)。然而,对于配体-H的去质子化过程,阴离子配体的促进能力顺序为Cl~-阴离子配体选择的指导和建议。
The Au(Ⅰ)-catalyzed cyclization reaction of indole is used to explore the effects of anion ligands on the proton-transfer process. Calculated results indicate that the anion ligands Cl~-, OTf~- and BF_4~- can greatly reduce the energy barrier of proton migration as proton-transfer shuttle. More importantly, our calculations discover that the Bronsted basicity of anion ligands(Cl~- > OTf~- > BF_4~-) is the primary reason that leads to the difference of ligand catalytic activity for the proton-transfer process. In the protonation of anion ligand, the catalytic capacities of anion ligands show significant difference according to the series Cl~- > OTf~- > BF_4~-, but the catalytic ability order of anion ligands is Cl~- < OTf~- < BF_4~- for the deprotonation of ligand-H. In a word, our calculations put forward some guidance and advice for the selection of anion ligands in the transition metal-catalyzed reactions including the proton-transfer process.
The Au(Ⅰ)-catalyzed cyclization reaction of indole is used to explore the effects of anion ligands on the proton-transfer process. Calculated results indicate that the anion ligands Cl~-, OTf~- and BF_4~- can greatly reduce the energy barrier of proton migration as proton-transfer shuttle. More importantly, our calculations discover that the Bronsted basicity of anion ligands(Cl~- > OTf~- > BF_4~-) is the primary reason that leads to the difference of ligand catalytic activity for the proton-transfer process. In the protonation of anion ligand, the catalytic capacities of anion ligands show significant difference according to the series Cl~- > OTf~- > BF_4~-, but the catalytic ability order of anion ligands is Cl~- < OTf~- < BF_4~- for the deprotonation of ligand-H. In a word, our calculations put forward some guidance and advice for the selection of anion ligands in the transition metal-catalyzed reactions including the proton-transfer process.
引文
[1]Chen,B.;Fan,W.;Chai,G.;Ma,S.Org.Lett.2012,14,3616.