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1
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37349005457
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For recent reviews on asymmetric organocatalytic Mannich reactions, see: a
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For recent reviews on asymmetric organocatalytic Mannich reactions, see: a) A. Ting, S. E. Schaus, Eur. J. Org. Chem. 2007, 5797;
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c) W. Notz, K. Sakthivel, T. Bui, G. Zhong, C. F. Barbas III, Tetrahedron Lett. 2001, 42, 199;
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d) A. Córdova, S. Watanabe, F. Tanaka, W. Notz, C. F. Barbas III, J. Am. Chem. Soc. 2002, 124, 1866;
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e) Y. Hayashi, W. Tsuboi, I. Ashimine, T. Urushima, M. Shoji, K. Sakai, Angew. Chem. 2003, 115, 3805;
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For reviews on asymmetric aminocatalysis, see: a
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For reviews on asymmetric aminocatalysis, see: a) C. F. Barbas III, Angew. Chem. 2008, 120, 44;
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Barbas III, C.F.1
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b) P. Melchiorre, M. Marigo, A. Carlone, G. Bartoli, Angew. Chem. 2008, 120, 6232;
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c) S. Mukherjee, J. W. Yang, S. Hoffmann, B. List, Chem. Rev. 2007, 107, 5471;
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b) J. Franzén, M. Marigo, D. Fielenbach, T. C. Wabnitz, A. Kjærsgaard, K. A. Jørgensen, J. Am. Chem. Soc. 2005, 127, 18296;
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c) T. Kano, Y. Yamaguchi, O. Tokuda, K. Maruoka, J. Am. Chem. Soc. 2005, 127, 16408;
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d) S. Mitsumori, H. Zhang, P. H.-Y. Cheong, K. N. Houk, F. Tanaka, C. F. Barbas III, J. Am. Chem. Soc. 2006, 128, 1040;
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e) H. Zhang, S. Mitsumori N. Utsumi, M. Imai, N. Garcia-Delgado, M. Mifsud, K. Albertshofer, P. H.-Y. Cheong, K. N. Houk, F. Tanaka, C. F. Barbas III, J. Am. Chem. Soc. 2008, 130, 875.
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22
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For an explanation of the origin of the anti selectivity observed in the direct asymmetric Mannich reaction catalyzed by 1, see: f I. Ibrahem, A. Córdova, Chem. Commun. 2006, 1760.
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For an explanation of the origin of the anti selectivity observed in the direct asymmetric Mannich reaction catalyzed by 1, see: f) I. Ibrahem, A. Córdova, Chem. Commun. 2006, 1760.
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23
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a) J. W. Yang, M. Stadler, B. List, Angew. Chem. 2007, 119, 615;
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See also: b
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See also: b) J. Vesely, R. Rios, I. Ibrahem, A. Córdova, Tetrahedron Lett. 2007, 48, 421.
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Vesely, J.1
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Córdova, A.4
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26
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33751325872
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For the first proline-catalyzed asymmetric Mannich reaction of a ketone and N-Boc imines (two examples), see: c) D. Enders, C. Grondal, M. Vrettou, Synthesis 2006, 3597.
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For the first proline-catalyzed asymmetric Mannich reaction of a ketone and N-Boc imines (two examples), see: c) D. Enders, C. Grondal, M. Vrettou, Synthesis 2006, 3597.
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27
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28444495479
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For a comprehensive review on the usefulness of α-amido sulfones, see
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For a comprehensive review on the usefulness of α-amido sulfones, see: M. Petrini, Chem. Rev . 2005, 105, 3949.
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Petrini, M.1
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33749820847
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For meaningful examples, see: a
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For meaningful examples, see: a) F. Fini, V. Sgarzani, D. Pettersen, R. P. Herrera, L. Bernardi, A. Ricci, Angew. Chem. 2005, 117, 8189;
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b) C. Palomo, M. Oiarbide, A. Laso, R. Lopez, J. Am. Chem. Soc. 2005, 127, 17622;
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N-carbamate-protected α-imino esters are known to be unstable, and their use in organic synthesis has been rather limited. Generally, they must be used immediately after their preparation; see, for example: a Y. Nakamura, R. Matsubara, H. Kiyohara, S. Kobayashi, Org. Lett. 2003, 5, 2481.
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N-carbamate-protected α-imino esters are known to be unstable, and their use in organic synthesis has been rather limited. Generally, they must be used immediately after their preparation; see, for example: a) Y. Nakamura, R. Matsubara, H. Kiyohara, S. Kobayashi, Org. Lett. 2003, 5, 2481.
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For an asymmetric organocatalytic Mannich reaction of Boc-imino ester, generated in situ by following the procedure developed by Kobayashi, see: b
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For an asymmetric organocatalytic Mannich reaction of Boc-imino ester, generated in situ by following the procedure developed by Kobayashi, see: b) T. B. Poulsen, C. Alemparte, S. Saaby, M. Bella, K. A. Jørgensen, Angew. Chem. 2005, 117, 2956;
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Poulsen, T.B.1
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Jørgensen, K.A.5
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3, 24 h, 65 % yield, 84:16 d.r. and 85 % ee; compare with entry 2 in Table 1).
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3, 24 h, 65 % yield, 84:16 d.r. and 85 % ee; compare with entry 2 in Table 1).
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55249122196
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Aminocatalytic Mannich strategies are limited to N-Boc-protected imines; see Ref. [5]. Extension of our method to Fmoc-protected aminosulfone (Fmoc = 9-fluorenylmethyloxycarbonyl) failed under the reported reaction conditions.
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Aminocatalytic Mannich strategies are limited to N-Boc-protected imines; see Ref. [5]. Extension of our method to Fmoc-protected aminosulfone (Fmoc = 9-fluorenylmethyloxycarbonyl) failed under the reported reaction conditions.
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a) J. W. Yang, C. Chandler, M. Stadler, D. Kampen, B. List, Nature 2008, 452, 453.
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Nature
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Yang, J.W.1
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For a review, see: b
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For a review, see: b) B. Alcaide, P. Almendros, Angew. Chem. 2008, 120, 4710;
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Angew. Chem
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Alcaide, B.1
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55249099181
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Under the reported conditions, in situ generated cyclohexyl imine reacts very slowly, albeit with high stereocontrol (1 week, 12 % conversion, 95:5 d.r., 98 % ee). Studies are focusing on the identification of a more active catalytic system.
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Under the reported conditions, in situ generated cyclohexyl imine reacts very slowly, albeit with high stereocontrol (1 week, 12 % conversion, 95:5 d.r., 98 % ee). Studies are focusing on the identification of a more active catalytic system.
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