What are the pKa values of C-H bonds in aromatic heterocyclic compounds in DMSO?

被引：358

作者：

Shen, Kuang ^{[1
]}

Fu, Yao ^{[1
]}

Li, Jia-Ning ^{[1
]}

Liu, Lei ^{[1
]}

Guo, Qing-Xiang ^{[1
]}

机构：

[1] Univ Sci & Technol China, Dept Chem, Anhui 230026, Peoples R China

来源：

TETRAHEDRON | 2007年 / 63卷 / 07期

基金：

中国国家自然科学基金;

关键词：

D O I：

10.1016/j.tet.2006.12.032

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A first-principle method has been successfully developed for the prediction of pK(a) values of aromatic heterocyclic compounds in DMSO solution with a precision of 1.1 pK(a) units. Comparison of theoretical results and experimental data (where available) also shows excellent consistency. Armed with this useful approach, the pKa values for a series of aromatic heterocycles were calculated in DMSO. Moreover, a discussion of the relationships between hydrogen acidities and molecular structures is conducted for the first time (determinants of C-H acidities, substituent effects, and some practical use of dehydrometalation). These statistics could be useful for synthetic chemists to design proper routes for introduction of aromatic heterocyclic moiety, especially when dehydrometalation reactions are used. (c) 2007 Elsevier Ltd. All rights reserved.

引用

页码：1568 / 1576

页数：9

共 71 条

[1] New density functional and atoms in molecules method of computing relative pKa values in solution [J].

Adam, KR .

JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (49) :11963-11972

[2] Site of ionization of polyfunctional bases and acids .1. Ab initio proton affinities [J].

Bagno, A ;

Scorrano, G .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (05) :1536-1544

[3] EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION [J].

BORDWELL, FG .

ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) :456-463

[4] Critical test of performance of B3LYP functional for prediction of gas-phase acidities and basicities [J].

Burk, P ;

Koppel, IA ;

Koppel, I ;

Leito, I ;

Travnikova, O .

CHEMICAL PHYSICS LETTERS, 2000, 323 (5-6) :482-489

[5] Metalated heterocycles and their applications in synthetic organic chemistry [J].

Chinchilla, R ;

Nájera, C ;

Yus, M .

CHEMICAL REVIEWS, 2004, 104 (05) :2667-2722

[6] A 10-STEP, ASYMMETRIC-SYNTHESIS OF (S)-CAMPTOTHECIN [J].

COMINS, DL ;

BAEVSKY, MF ;

HONG, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (27) :10971-10972

[7] ORTHO LITHIATION OF 2-METHOXYPYRIDINES, 3-METHOXYPYRIDINES, AND 4-METHOXYPYRIDINES [J].

COMINS, DL ;

LAMUNYON, DH .

TETRAHEDRON LETTERS, 1988, 29 (07) :773-776

[8] Implicit solvation models: Equilibria, structure, spectra, and dynamics [J].

Cramer, CJ ;

Truhlar, DG .

CHEMICAL REVIEWS, 1999, 99 (08) :2161-2200

[9] Gaussian-3 (G3) theory for molecules containing first and second-row atoms [J].

Curtiss, LA ;

Raghavachari, K ;

Redfern, PC ;

Rassolov, V ;

Pople, JA .

JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (18) :7764-7776

[10] THE C-H BOND-ENERGY OF BENZENE [J].

DAVICO, GE ;

BIERBAUM, VM ;

DEPUY, CH ;

ELLISON, GB ;

SQUIRES, RR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (09) :2590-2599

← 1 2 3 4 5 6 7 8 →