Using the Pyridine and Quinuclidine Scaffolds for Superbases: A DFT Study

被引：34

作者：

Bachrach, Steven M. ^{[1
]}

Wilbanks, Cecily C. ^{[1
]}

机构：

[1] Trinity Univ, Dept Chem, San Antonio, TX 78212 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2010年 / 75卷 / 08期

关键词：

ORGANIC SUPERBASES; PROTON AFFINITY; HYDROGEN-BONDS; MOLECULES; POLYAMINOPHOSPHAZENES; MICROSOLVATION; DERIVATIVES; SPONGES; DESIGN; BASES;

D O I：

10.1021/jo100295s

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

2,6-Disubstituted pyridines and 2,6,7-trisubstituted quinuclidines are screened as potential strong bases. The relative proton affinities of the bases are computed at PBE1PBE/6-311 G(d,p) in the gas phase and in the solution phase (THF) at the same level with the IEFPCM treatment. Basicities are enhanced by the lone-pair possessing atoms on the substituents' arms stabilizing the conjugate acid through hydrogen bonding. The strongest bases are 2,6-bis(3-methoxy-2-furyl)-4-dimethylaminopyridine and 2,6-di(2-dimethylaminoethyl)pyridine

引用

页码：2651 / 2660

页数：10

共 40 条

[1] Toward reliable density functional methods without adjustable parameters: The PBE0 model
Adamo, C
Barone, V
[J]. JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) : 6158 - 6170
[2] AJEET S, 2007, EUR J CHEM, P420
[3] Design of C2-chiral diamines that are computationally predicted to be a million-fold more basic than the original proton sponges
Alder, RW
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (21) : 7924 - 7931
[4] ALDER RW, 1968, CHEM COMMUN, P723
[5] Microsolvation of glycine: A DFT study
Bachrach, Steven M.
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2008, 112 (16) : 3722 - 3730
[6] Microsolvation of Cysteine: A Density Functional Theory Study
Bachrach, Steven M.
Nguyen, Thuy T.
Demoin, Dustin W.
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2009, 113 (21) : 6172 - 6181
[7] COUTURIER Y, 1992, B SOC CHIM FR, V129, P335
[8] Derivatives of azacalix[3](2,6)pyridine are strong neutral organic superbases: A DFT study
Despotovic, I.
Kovacevic, B.
Maksic, Z. B.
[J]. ORGANIC LETTERS, 2007, 9 (06) : 1101 - 1104
[9] Pyridine and s-triazine as building blocks of nonionic organic superbases -: a density functional theory B3LYP study
Despotovic, Ines
Kovacevic, Borislav
Maksic, Zvonimir B.
[J]. NEW JOURNAL OF CHEMISTRY, 2007, 31 (03) : 447 - 457
[10] Rational design and first principles studies toward the discovery of a small and versatile proton sponge
Estrada, E
Simón-Manso, Y
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (11) : 1719 - 1721

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