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This scenario parallels "ligand-accelerated catalysis" (LAC). By combining the proton (stemming from the Brønsted acid) and the (catalytically inactive) chiral molecule, an equilibrium mixture results in which the active catalyst formed consists of a proton bound to a chiral ligand; for a review on LAC, see: D. J. Berrisford, C. Bolm, K. B. Sharpless, Angew. Chem. 1995, 107, 1159; Angew. Chem. Int. Ed. Engl. 1995, 34, 1059.
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Reference [11c] gives an excellent background to the current studies and highlights the many contributions published by other researchers, which finally led to the development of the present asymmetric acid-base catalysts; for further details, this review is highly recommended.
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The salts were prepared by first reacting diamine 9a with excess (> 2 equiv) TfOH. The resulting diammonium salt was then mixed with an additional equimolar amount of diamine 9a to yield the desired amine-acid of composition 15. Any variation of this ratio resulted in a decrease of the reaction rate. For example, a salt with a 1:2 (amine/acid) stoichiometry did not show any catalytic activity.
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A protonated chiral pyrrolidine has also been used in catalyzed asymmetric epoxidations. In this case, however, it appears to only serve as carrier and activator of the peroxymonosulfate anion, and no additional interaction with the olefinic substrate has been described: V. K. Aggarwal, C. Lopin, F. Sandrinelli, J. Am. Chem. Soc. 2003, 125, 7596, and references therein.
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note
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The authors report that the use of the chiral ligand alone furnished a result comparable to the uncatalyzed reaction (less than 5% yield at -20°C after 5 days).
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After the reports by MacMillan, imidazolidinone catalysts were also applied by other groups; for examples, see: a) - [4+3] cycloadditions: M. Harmata, S. K. Ghosh, X. Hong, S. Wacharasindhu, P. Kirchhöfer, J. Am. Chem. Soc. 2003, 125, 2058; b) intramolecular Michael reactions: M. T. Hechavarria Fonseca, B. List, Angew. Chem. 2004, 116, 4048; Angew. Chem. Int. Ed. 2004, 43, 3958; c) tranfer hydrogenations: J. W. Yang, M. T. Hechavarria Fonseca, N. Vignola, B. List, Angew. Chem. 2005, 117, 110; Angew. Chem. Int. Ed. 2005, 44, 108.
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After the reports by MacMillan, imidazolidinone catalysts were also applied by other groups; for examples, see: a) - [4+3] cycloadditions: M. Harmata, S. K. Ghosh, X. Hong, S. Wacharasindhu, P. Kirchhöfer, J. Am. Chem. Soc. 2003, 125, 2058; b) intramolecular Michael reactions: M. T. Hechavarria Fonseca, B. List, Angew. Chem. 2004, 116, 4048; Angew. Chem. Int. Ed. 2004, 43, 3958; c) tranfer hydrogenations: J. W. Yang, M. T. Hechavarria Fonseca, N. Vignola, B. List, Angew. Chem. 2005, 117, 110; Angew. Chem. Int. Ed. 2005, 44, 108.
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The activation of the unsaturated carbonyl compound is suggested to originate from a lowering of the LUMO upon conversion of the substrate into the corresponding, and much more reactive, iminium ion.
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Triflic acid was more effective than the weaker methanesulfonic acid in generating an active Diels-Alder catalyst.
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83
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17044387026
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3 complexes of methyl cinnamate, benzylidene acetone, and dibenzylidene acetone, in which the short distances between the α-olefinic hydrogen atom and the nearest fluorine atom suggests such an attractive interaction.
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84
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17044439119
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note
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[35c]
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85
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17044387820
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[13] should be mentioned again.
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