AbstractAbstract
[en] Cinchona-based bifunctional catalysts have been extensively employed in the field of organocatalysis due to the incorporation of both hydrogen-bonding acceptors (quinuclidine) and hydrogen-bonding donors (e. g., alcohol, amide, (thio)urea and squaramide) in the molecule, which can simultaneously activate nucleophiles and electrophiles, respectively. Among them, cinchona-derived (thio)urea and squaramide catalysts have shown remarkable application potential by using their bifurcated hydrogen bonding donors in activating electrophilic carbonyls and imines. However, due to their bifunctional nature, they tend to aggregate via inter-and intramolecular acid-base interactions under certain conditions, which can lead to a decrease in the enantioselectivity of the reaction. To overcome this self-aggregation problem of bifunctional organocatalysts, we have successfully developed a series of sulfonamide-based organocatalysts, which do not aggregate under conventional reaction conditions. Herein, we summarize the recent applications of our cinchona-derived sulfonamide organocatalysts in highly enantioselective methanolytic desymmetrization and decarboxylative aldol reactions. Immobilization of sulfonamide-based catalysts onto solid supports allowed for unprecedented practical applications in the synthesis of valuable bioactive synthons with excellent enantioselectivities
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32 refs, 27 figs
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Journal Article
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Bulletin of the Korean Chemical Society; ISSN 0253-2964; ; v. 35(6); p. 1590-1600
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[en] The use of ionic liquids as reaction media can confer many advantages upon catalytic reactions over reactions in organic solvents. In ionic liquids, catalysts having polar or ionic character can easily be immobilized without additional structural modification and thus the ionic solutions containing the catalyst can easily be separated from the reagents and reaction products, and then, be reused. More interestingly, switching from an organic solvent to an ionic liquid often results in a significant improvement in catalytic performance (e.g., rate acceleration, (enantio)selectivity improvement and an increase in catalyst stability). In this review, some recent interesting results which can nicely demonstrate these positive 'ionic liquid effect' on catalysis are discussed
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71 refs, 27 figs, 1 tab
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Journal Article
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Bulletin of the Korean Chemical Society; ISSN 0253-2964; ; v. 26(9); p. 1321-1330
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[en] We have been prepared a novel P,N,N,P-tetradentate Ru-complex by reaction of bisphosphinobisoxazoline, Phos-Biox, with either RuCl2(DMSO)2 or RuCl2(PPh3)3. This complex acts as a catalyst for transfer hydrogenation of aromatic ketones. However, additional PPh3 is necessary for asymmetric induction. In the past decade, oxazoline-based bidentate ligands have proven very valuable in asymmetric catalysis, mainly as heterotoditopic ligands, such as the phosphino-oxazoline III or as bis(oxazoline) ligands with or without a coordinating connecting group. In contrast to the bidentate or tridentate ligands, chiral tetradentate bis(oxazolinyl)-type ligands have been less extensively developed
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7 refs, 1 fig, 1 tab
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Journal Article
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Bulletin of the Korean Chemical Society; ISSN 0253-2964; ; v. 24(9); p. 1407-1409
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[en] We report a quantum chemical study of an extremely efficient nucleophilic aromatic fluorination in molten salts. We describe that the mechanism involves solvent anion interacting with the ion pair nucleophile M+F- (M = Na, K, Rb, Cs) to accelerate the reaction. We show that our proposed mechanism may well explain the excellent efficiency of molten salts for SNAr reactions, the relative efficacy of the metal cations, and also the observed large difference in rate constants in two molten salts (n-C4H9)4N+ CX3SO3-, (X=H, F) with slightly different sidechain (-CH3 vs. -CF3)
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36 refs, 3 figs, 1 tab
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Journal Article
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Bulletin of the Korean Chemical Society; ISSN 0253-2964; ; v. 33(3); p. 881-884
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