Density Functional Theory Study of Selective Deacylation of Aromatic Acetate in the Presence of Aliphatic Acetate under Ammonium Acetate Mediated Conditions

被引：4

作者：

Xia, Shijing ^{[1
]}

Zhang, Haoyu ^{[2
]}

机构：

[1] Dow Chem Co USA, Engn & Proc Sci R&D, Midland, MI 48674 USA

[2] Dow Chem Co USA, Analyt Technol Ctr, Midland, MI 48674 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 79卷 / 13期

关键词：

P-NITROPHENYL ACETATE; ACYL TRANSFER; DEPROTECTION; HYDROLYSIS; MECHANISMS;

D O I：

10.1021/jo500855g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Aromatic acetates can be selectively deprotected in the presence of aliphatic acetates under ammonium acetate mediated condition. B3LYP/6-31++G** level of theory was demonstrated to be successfully used to model the relative reaction rates for deacylation reactions for aliphatic and aromatic ester systems. On the basis of the mechanistic studies, acetate anion is most likely to be the active catalyst for the ester deacylation reactions under ammonium acetate mediated condition.

引用

页码：6135 / 6142

页数：8

共 18 条

[1]

[Anonymous], 2011, OLI STREAM AN 2 0

[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[3]

BUNTON CA, 1967, CHEM IND-LONDON, P1835

[4] Nucleophilic displacement at the benzoyl centre: A study of the change in geometry at the carbonyl carbon atom [J].

Colthurst, MJ ;

Williams, A .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1997, (08) :1493-1497

[5] The functional relation between the constants of the Arrhenius equation. [J].

Fairclough, RA ;

Hinshelwood, CN .

JOURNAL OF THE CHEMICAL SOCIETY, 1937, :538-546

[6]

Frisch M. J., 2016, Gaussian 03 Revision B.03

[7] CONCERTED OR STEPWISE MECHANISMS FOR ACYL TRANSFER-REACTIONS OF P-NITROPHENYL ACETATE - TRANSITION-STATE STRUCTURES FROM ISOTOPE EFFECTS [J].

HENGGE, AC ;

HESS, RA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (25) :11256-11263

[8] Isotope effects on enzyme-catalyzed acyl transfer from p-nitrophenyl acetate:: Concerted mechanisms and increased hyperconjugation in the transition state [J].

Hess, RA ;

Hengge, AC ;

Cleland, WW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (12) :2703-2709

[9]

Labanowski JanK., 1991, DENSITY FUNCTIONAL M

[10] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY [J].

LEE, CT ;

YANG, WT ;

PARR, RG .

PHYSICAL REVIEW B, 1988, 37 (02) :785-789

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