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a) For an important early review on the subject, see: J. T. Welch, Tetrahedron 1987, 43, 3123;
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Welch, J.T.1
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b) Special Issue on "Fluorine in the Life Sciences", ChemBioChem 2004, 5, 557-726.
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For a recent Review on selectfluor, see: P. T. Nyffeler, S. G. Durón, M. D. Burkart, S. P. Vincent, C.-H. Wong, Angew. Chem. 2005, 117, 196;
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Nyffeler, P.T.1
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reference [1a]
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For reviews of electrophilic fluorinating agents, see: a) reference [1a];
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Y. Hamashima, K. Yagi, H. Takano, L. Tamas, M. Sodeoka, J. Am. Chem. Soc. 2002, 124, 14530.
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b) Cu and Ni: N. Shibata, T. Ishimaru, T. Nagai, J. Kohno, T. Toru, Synlett 2004, 1703;
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II complexes in enantioselective fluorination has been described in a recent review: H. Ibrahim, A. Togni, Chem. Commun. 2004, 1147;
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Ibrahim, H.1
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d) for an informative and up-to-date review on the development of enantioselective fluorination reactions, see: J.-A. Ma, D. Cahard, Chem. Rev. 2004, 104, 6119;
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b) N. Shibata, E. Suzuki, Y. Takeuchi, J. Am. Chem. Soc. 2000, 122, 10728;
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31044433329
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see reference [8d]
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The cinchona alkaloid mediated enantioselective fluorination can be equally well performed with N-fluoro cinchona alkaloid (Shibata et al.) or with the isolated N-fluoroammonium salts (Cahard et al.) generated in situ. For highly informative discussions, see reference [8d].
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M. Marigo, D. Fielenbach, A. Braunton, A. Kjærsgaard, K. A. Jørgensen, Angew. Chem. 2005, 117, 3769;
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The higher reactivity of aldehydes over ketones in enamine catalysis has been documented in aldol, α-amination, and α-oxygenation processes: P. I. Dalko, L. Moisan, Angew. Chem. 2004, 116, 5248;
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With the exception of the study by Barbas and co-workers, all α-fluoroaldehydes were immediately reduced to the corresponding α-fluoroalcohols 13 owing to the instability and volatility of the aldehyde products; see: F. A. Davis, P. V. N. Kasu, G. Sundarababu, H. Qi, J. Org. Chem. 1997, 62, 7546.
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For examples, see: M. Marigo, T. C. Wabnitz, D. Fielenbach, K. A. Jørgensen, Angew. Chem. 2005, 117, 804;
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N. Shibata, J. Kohno, K. Takai, T. Ishimaru, S. Nakamura, T. Toru, S. Kanemasa, Angew. Chem. 2005, 117, 4276;
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31044431849
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A direct comparison of metal catalysts and organocatalysts is provided by the recently published studies on the examination of β-ketoesters. The α-amination products can be obtained in up to 90% ee by using cinchona alkaloids as catalysts: a) S. Saaby, M. Bella, K. A. Jørgensen, J. Am. Chem. Soc. 2004, 126, 8120;
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0142131252
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II-bisoxazoline complexes afford the α-amination products in outstanding enantioselectivity (up to 99% ee in many cases): c) M. Marigo, K. Juhl, K. A. Jørgensen, Angew. Chem. 2003, 115, 1405;
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Angew. Chem. Int. Ed. 2003, 42, 1367; clearly, other factors such as chemoselectivity, reaction rate, ease of operation, and cost of the catalyst are also issues that need to be taken into account in selecting the asymmetric catalyst.
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