The DMAP-catalyzed acetylation of alcohols - A mechanistic study (DMAP=4-(dimethylamino)pyridine)

Xu SJ; Held I; Kempf B; Mayr H; Steglich W; Zipse H

首页> 外文期刊>Chemistry: A European journal >The DMAP-catalyzed acetylation of alcohols - A mechanistic study (DMAP=4-(dimethylamino)pyridine)

【24h】

The DMAP-catalyzed acetylation of alcohols - A mechanistic study (DMAP=4-(dimethylamino)pyridine)

机译：DMAP催化的醇的乙酰化-机理研究（DMAP = 4-（二甲基氨基）吡啶）

获取原文

获取原文并翻译 | 示例

掌桥外文数据库（机构版） >>

开具论文收录证明 >>

文献代查 >>

页面导航

摘要
著录项
相似文献
相关主题

摘要

The acetylation of tert-butanol with acetic anhydride catalyzed by 4-(dimethylamino)pyridine (DMAP) has been studied at the Becke3LYP/6311+G(d,p)//Becke3LYP/6-3IG(d) level of theory. Solvent effects have been estimated through single-point calculations with the PCM/UAHF solvation model. The energetically most favorable pathway proceeds through nucleophilic attack of DMAP at the anhydride carbonyl group and subsequent formation of the corresponding acetylpyridinium/acetate ion pair. Resubstrate yields the final product, tert-butylacetate. The competing base-catalyzed reaction pathway can either proceed in a concerted or in a stepwise manner. In both cases the reaction barrier far exceeds that of the nucleophilic catalysis mechanism. The reaction mechanism has also been studied experimentally in dichloromethane through analysis of the reaction kinetics for the acetylation of cyclohexanol with acetic anhydride, in the presence of DMAP as catalyst and triethylamine as the auxiliary base. The reaction is found to be first-order with respect to acetic anhydride, cyclohexanol, and DMAP, and zero-order with respect to triethyl amine. Both the theoretical as well as the experimental studies strongly support the nucleophilic catalysis pathway.

机译：在Becke3LYP / 6311 + G（d，p）// Becke3LYP / 6-3IG（d）的理论水平上研究了4-（二甲基氨基）吡啶（DMAP）催化的丁醇与乙酸酐的乙酰化反应。已经通过使用PCM / UAHF溶剂化模型进行单点计算来估计溶剂效果。能量上最有利的途径是通过DMAP在酸酐羰基上的亲核攻击并随后形成相应的乙酰基吡啶/乙酸根离子对来进行的。重底物产生最终产物乙酸叔丁酯。竞争性碱催化的反应途径可以协同或逐步进行。在这两种情况下，反应障碍都远远超过亲核催化机理。还通过在二氯甲烷中以DMAP为催化剂，三乙胺为辅助碱的条件下，分析了环己醇与乙酸酐乙酰化的反应动力学，在二氯甲烷中进行了实验研究。发现该反应相对于乙酸酐，环己醇和DMAP为一级，相对于三乙胺为零级。理论研究和实验研究都强烈支持亲核催化途径。

著录项

来源
《Chemistry: A European journal》 |2005年第16期|共7页
作者
Xu SJ; Held I; Kempf B; Mayr H; Steglich W; Zipse H;
展开▼
作者单位

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类
关键词
acylation; density functional calculations; dimethylaminopyridine; kinetics; nucleophilic catalysis; P-NITROPHENYL ACETATE; CHIRAL NUCLEOPHILIC CATALYSTS; PHENOLATE ION NUCLEOPHILES; ACYL GROUP-TRANSFER; KINETIC RESOLUTION; TRANSITION-STATE; ASYMMETRIC CATALYSIS; ACYLATION CATALYSTS; ENANTIOSELECTIVE SYNTHESIS; NONENZYMATIC ACYLATION;

机译：酰化;密度泛函计算;二甲氨基吡啶;动力学;亲核催化;乙酸对硝基苯酯;手性核催化剂;酚离子核;酰基转移;动力学拆分;过渡态;乙酰化;烯丙基化;

相似文献

外文文献
中文文献
专利

1. The DMAP-catalyzed acetylation of alcohols - A mechanistic study (DMAP=4-(dimethylamino)pyridine) [J] . Xu SJ, Held I, Kempf B, Chemistry: A European journal . 2005,第16期

机译：DMAP催化的醇的乙酰化-机理研究（DMAP = 4-（二甲基氨基）吡啶）
2. Reactions of an iron chlorodistannane with hydroxide: Isolation and structural characterization of {(η~5-Me_3SiC _5H_4)Fe(CO)[(SntBu_2) _2(μ-OH)]···DMAP}, DMAP = 4-(N, N -dimethylamino)pyridine, a μ-OH-stannyl(stannylene)-iron complex [J] . Sharma H.K., Metta-Maga?a A.J., Pannell K.H. Organometallics . 2013,第21期

机译：氯二氢萘铁与氢氧化物的反应：{（η〜5-Me_3SiC _5H_4）Fe（CO）[（SntBu_2）_2（μ-OH）]···DMAP}的分离和结构表征，DMAP = 4-（N， N-二甲基氨基）吡啶，μ-OH-锡烷基（亚锡烷基）-铁络合物
3. Preparation and Structure of [RhCl(nbd)(dmap)](nbd=dicyclo[2.2.1]hepta-2,5-diene;dmap=4-(N,N-dimethylamino)pyridine) [J] . Yasumasa Takenaka, Kohtaro osakada Bulletin of the Chemical Society of Japan . 2000,第1期

机译：[RhCl（nbd）（dmap）]的制备与结构（nbd =二环[2.2.1]庚-2,5-二烯; dmap = 4-（N，N-二甲基氨基）吡啶）
4. Effects of molecular charge density polarization on x~((1)) and x~((2)): a computational study of 2-methyl-4-nitroaniline (MNA) and 4-(N,N-dimethylamino)-3-acetamidonitrobenzene (DAN) [C] . T. Seidler, K. Stadnicka, B. Champagne Optical processes in organic materials and nanostructures II . 2013

机译：分子电荷密度极化对x〜（（1））和x〜（（2））的影响：2-甲基-4-硝基苯胺（MNA）和4-（N，N-二甲基氨基）-3-的计算研究乙酰氨基硝基苯（DAN）
5. Electrochemical Investigation of Gold Nanoparticles Stabilized with 4-(Dimethylamino)pyridine. [D] . Lemay, Denis M. 2011

机译：4-（二甲氨基）吡啶稳定的金纳米粒子的电化学研究。
6. DMAP-Catalyzed One-Pot Synthesis of Quinazoline-24-dionesfrom 2-Aminobenzamides and Di-tert-butyl Dicarbonate [O] . Hui Chen, Peng Li, Rongfei Qin, 2020

机译：DMAP催化一锅法合成喹唑啉-24-二酮2-氨基苯甲酰胺和二碳酸二叔丁酯
7. A Study for Kinetics and Oxidation Reaction of Alcohols by Cr(VI)-4-(Dimethylamino)pyridine [O] . Young-Sik Kim, Young-Cho Park, Young Jun Kim 2013

机译：Cr（VI）-4-（二甲基氨基）吡啶醇的动力学和氧化反应研究

The DMAP-catalyzed acetylation of alcohols - A mechanistic study (DMAP=4-(dimethylamino)pyridine)

摘要

著录项

相似文献

相关主题

期刊订阅