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For reviews on the asymmetric Mannich reaction, see: (a) Benaglia, M.; Cinquini, M.; Cozzi, F. Eur. J. Org. Chem. 2000, 4, 563-572. (b) Denmark, S.; Nicaise, J.-C. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 2, pp 954-957. (c) Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069-1094.
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For reviews on the asymmetric Mannich reaction, see: (a) Benaglia, M.; Cinquini, M.; Cozzi, F. Eur. J. Org. Chem. 2000, 4, 563-572. (b) Denmark, S.; Nicaise, J.-C. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 2, pp 954-957. (c) Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069-1094.
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Kobayashi, S.1
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For recent reports on the catalytic asymmetric Mannich reaction in the synthesis of β-amino acid derivatives, see: (a) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 8180-8136. (b) Xue, S.; Yu, S.; Deng, Y.; Wulff, W. D. Angew. Chem., Int. Ed. 2001, 40, 2271-2274. (c) Córdova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, 1866-1867. (d) Kobayashi, S.; Matsubara, R.; Kitagawa, H. Org. Lett. 2002, 4, 143-145.
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For recent reports on the catalytic asymmetric Mannich reaction in the synthesis of β-amino acid derivatives, see: (a) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 8180-8136. (b) Xue, S.; Yu, S.; Deng, Y.; Wulff, W. D. Angew. Chem., Int. Ed. 2001, 40, 2271-2274. (c) Córdova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, 1866-1867. (d) Kobayashi, S.; Matsubara, R.; Kitagawa, H. Org. Lett. 2002, 4, 143-145.
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For recent reports on the catalytic asymmetric Mannich reaction in the synthesis of β-amino acid derivatives, see: (a) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 8180-8136. (b) Xue, S.; Yu, S.; Deng, Y.; Wulff, W. D. Angew. Chem., Int. Ed. 2001, 40, 2271-2274. (c) Córdova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, 1866-1867. (d) Kobayashi, S.; Matsubara, R.; Kitagawa, H. Org. Lett. 2002, 4, 143-145.
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Watanabe, S.2
Tanaka, F.3
Notz, W.4
Barbas C.F. III5
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0037050504
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For recent reports on the catalytic asymmetric Mannich reaction in the synthesis of β-amino acid derivatives, see: (a) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 8180-8136. (b) Xue, S.; Yu, S.; Deng, Y.; Wulff, W. D. Angew. Chem., Int. Ed. 2001, 40, 2271-2274. (c) Córdova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Barbas, C. F., III. J. Am. Chem. Soc. 2002, 124, 1866-1867. (d) Kobayashi, S.; Matsubara, R.; Kitagawa, H. Org. Lett. 2002, 4, 143-145.
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For examples of alternative enantioselective catalytic routes to β-amino acid derivatives, see: (a) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperese, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (b) Myers J. K.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 8959-8960. (c) Nelson, S.; Spencer, K. L. Angew. Chem., Int. Ed. 2000, 39, 1323-1325. (d) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578-1579. (e) Zhou, Y.-G.; Tang, W.; Wang, W.-B.; Li, W.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 4952-4953. (f) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199.
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Liu, M.3
Jasperese, C.P.4
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0033615304
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For examples of alternative enantioselective catalytic routes to β-amino acid derivatives, see: (a) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperese, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (b) Myers J. K.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 8959-8960. (c) Nelson, S.; Spencer, K. L. Angew. Chem., Int. Ed. 2000, 39, 1323-1325. (d) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578-1579. (e) Zhou, Y.-G.; Tang, W.; Wang, W.-B.; Li, W.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 4952-4953. (f) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199.
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Jacobsen, E.N.2
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0034599875
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For examples of alternative enantioselective catalytic routes to β-amino acid derivatives, see: (a) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperese, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (b) Myers J. K.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 8959-8960. (c) Nelson, S.; Spencer, K. L. Angew. Chem., Int. Ed. 2000, 39, 1323-1325. (d) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578-1579. (e) Zhou, Y.-G.; Tang, W.; Wang, W.-B.; Li, W.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 4952-4953. (f) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199.
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Spencer, K.L.2
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0037181062
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For examples of alternative enantioselective catalytic routes to β-amino acid derivatives, see: (a) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperese, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (b) Myers J. K.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 8959-8960. (c) Nelson, S.; Spencer, K. L. Angew. Chem., Int. Ed. 2000, 39, 1323-1325. (d) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578-1579. (e) Zhou, Y.-G.; Tang, W.; Wang, W.-B.; Li, W.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 4952-4953. (f) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199.
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Fu, G.C.2
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For examples of alternative enantioselective catalytic routes to β-amino acid derivatives, see: (a) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperese, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (b) Myers J. K.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 8959-8960. (c) Nelson, S.; Spencer, K. L. Angew. Chem., Int. Ed. 2000, 39, 1323-1325. (d) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578-1579. (e) Zhou, Y.-G.; Tang, W.; Wang, W.-B.; Li, W.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 4952-4953. (f) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199.
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For examples of alternative enantioselective catalytic routes to β-amino acid derivatives, see: (a) Sibi, M. P.; Shay, J. J.; Liu, M.; Jasperese, C. P. J. Am. Chem. Soc. 1998, 120, 6615-6616. (b) Myers J. K.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 8959-8960. (c) Nelson, S.; Spencer, K. L. Angew. Chem., Int. Ed. 2000, 39, 1323-1325. (d) Hodous, B. L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 1578-1579. (e) Zhou, Y.-G.; Tang, W.; Wang, W.-B.; Li, W.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 4952-4953. (f) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199.
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0005182174
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note
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Other imine protecting groups examined under the same reaction conditions: N-Cbz benzaldimine, 26% ee; N-tosyl benzaldimine, 0% ee.
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32
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0005178040
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note
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The enantioselectivity of this reaction is relatively insensitive to dilution, stoichiometry, and rate of nucleophile addition. No change in enantioselectivity was observed with solvents of low polarity, while strongly polar aprotic solvents led to dramatically poorer ee's. Use of protic solvents resulted in rapid decomposition of the imine.
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9d
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34
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0005139085
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note
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While HMPA has traditionally been used as a cosolvent for tertbutyldimethylsilylation of lithium enolates, both DMPU or 1-methyl-2-pyrrolidinone (NMP) are effective alternatives.
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35
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0005214232
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note
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Full details of catalyst structure/enantioselectivity profiles for both the Mannich and the Strecker reactions will be reported in due course.
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36
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0005189233
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note
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Thiohydantoin formation proved problematic in the preparation of thiourea derivatives bearing secondary amides. Detailed experimental procedures are provided as Supporting Information.
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37
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0005231114
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note
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Aliphatic N-Boc imines have as yet not been investigated because no useful method currently exists for their synthesis.
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39
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0005150012
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Ph.D. Dissertation, Eidgenössische Technische Hochschule, Zürich, Switzerland
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Gademann, K. Ph.D. Dissertation, Eidgenössische Technische Hochschule, Zürich, Switzerland, 2000.
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Gademann, K.1
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