Oxygen superbases as polar binding pockets in nonpolar solvents
Jazyk angličtina Země Spojené státy americké Médium print
Typ dokumentu časopisecké články, práce podpořená grantem
PubMed
20722390
DOI
10.1021/ja103744f
Knihovny.cz E-zdroje
- MeSH
- 2,2'-dipyridyl analogy a deriváty chemie MeSH
- kyslík chemie MeSH
- molekulární struktura MeSH
- rozpouštědla chemie MeSH
- stereoizomerie MeSH
- termodynamika MeSH
- vazebná místa MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- 2,2'-bipyridyl-N,N'-dioxide MeSH Prohlížeč
- 2,2'-dipyridyl MeSH
- kyslík MeSH
- rozpouštědla MeSH
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.
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