Oxygen Superbases as Polar Binding Pockets in Nonpolar Solvents

被引：21

作者：

Duchackova, Lucie ^{[1
]}

Kadlcikova, Aneta ^{[1
]}

Kotora, Martin ^{[1
]}

Roithova, Jana ^{[1
]}

机构：

[1] Charles Univ Prague, Dept Organ Chem, Prague 12843 2, Czech Republic

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 36期

关键词：

AXIALLY CHIRAL GUANIDINE; KINETIC METHOD; PROTON AFFINITIES; ENANTIOSELECTIVE ALLYLATION; BIPYRIDINE N; N'-DIOXIDES; ALDEHYDES; BASICITY; ACTIVATION; CATALYSIS; ENERGIES;

D O I：

10.1021/ja103744f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A novel class of chiral superbases derived from the 2,2 '-bipyridyl-N,N-dioxide skeleton are presented. Combined experimental and theoretical data reveal that their proton affinities are on the order of 1050 kJ mol(-1), with protonation occurring at the oxygen atoms in a chelating manner. In the free bases, the oxygen atoms form a strongly polar binding site hidden in a hydrophobic envelope formed by the hydrocarbon backbone of the superbases. This chiral molecular structure can entrap polar intermediates or polarized transition structures and stabilize them in nonpolar solvents. Specifically, this mode of catalysis is shown for the coupling of benzaldehyde and allyltrichlorosilane.

引用

页码：12660 / 12667

页数：8

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