Nucleophilicities and carbon basicifies of pyridines

被引：123

作者：

Brotzel, Frank ^{[1
]}

Kempf, Bernhard ^{[1
]}

Singer, Thomas ^{[1
]}

Zipse, Hendrik ^{[1
]}

Mayr, Herbert ^{[1
]}

机构：

[1] Univ Munich, Dept Chem & Biochem, D-81377 Munich, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2007年 / 13卷 / 01期

关键词：

carbocations; intrinsic barriers; kinetics; organocatalysis; pyridines;

D O I：

10.1002/chem.200600941

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rate and equilibrium constants for the reactions of pyridines with donor-substituted benzhydrylium ions have been determined spectrophotometrically. The correlation equation log k(20 degrees C)=s(N+E), in which s and N are nucleophile-specific parameters and E is an electrophile-specific parameter, has been used to determine the nucleophilicity parameters of various pyridines in CH2Cl2 and aqueous solution and to compare them with N of other nucleophiles. It is found that the nucleophilic organocatalyst 4-(dimethylamino)pyridine (DMAP) and tertiary phosphanes have comparable nucleophilicities and carbon basicities despite widely differing Bronsted basicities. For that reason, these reactivity parameters are suggested as guidelines for the development of novel organocatalysts. ne Marcus equation is employed for the determination of the intrinsic barriers of these reactions.

引用

页码：336 / 345

页数：10

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