P. Dziedzic et al. / Tetrahedron Letters 49 (2008) 803–807
807
Barbas, C. F. J. Am. Chem. Soc. 2002, 124, 1866; (c) Munch, A.;
synthesis see: (b) Kazmaier, U. Angew. Chem., Int. Ed. 2005, 44, 2186;
(c) Limbach, M. Chem. Biodivers. 2005, 2, 825.
14. For the use of dihydroxyacetone in enantioselective amino acid
¨
Wendt, B.; Christmann, M. Synlett 2004, 2751; (d) Zhuang, W.;
Saaby, S.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2004, 43, 4476; (e)
Fustero, S.; Jimenez, D.; Sanz-Cervera, J. F.; Sanchez-Rosello, M.;
Esteban, E.; Simon-Fuentes, A. Org. Lett. 2005, 7, 3433; (f) Cobb, A.
J. A.; Shaw, D. M.; Ley, S. V. Synlett 2004, 558; (g) Cobb, A. J. A.;
Shaw, D. M.; Longbottom, D. A.; Gold, J. B.; Ley, S. V. Org. Biomol.
Chem. 2005, 3, 84; (h) List, B.; Pojarliev, P.; Biller, W. T.; Martin, H.
´
catalyzed direct aldol reactions see: (a) Dziedzic, P.; Zou, W.; Hafren,
´
´
J.; Cordova, A. Org. Biomol. Chem. 2006, 4, 38; (b) Cordova, A.; Zou,
W.; Dziedzic, P.; Ibrahem, I.; Reyes, E.; Xu, Y. Chem. Eur. J. 2006,
´
12, 5383; (c) Cordova, A.; Zou, W.; Dziedzic, P.; Ibrahem, I.; Reyes,
E.; Xu, Y. Chem. Eur. J. 2006, 12, 5175; (d) Ramasastry, S. S. V.;
Albertshofer, K.; Utsumi, N.; Tanaka, F.; Barbas, C. F., III. Angew.
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J. J. Am. Chem. Soc. 2002, 124, 827; (i) Ibrahem, I.; Cordova, A.
´
´
Chem. Commun. 2006, 1760; (j) Ibrahem, I.; Casas, J.; Cordova, A.
Chem., Int. Ed. 2007, 46, 5572; See also: (e) Cordova, A.; Notz, W.;
Angew. Chem., Int. Ed. 2004, 43, 6528; (k) Ibrahem, I.; Zou, W.;
Barbas, C. F., III. Chem. Commun. 2002, 3024; (f) Kofoed, J.;
Reymond, J.-L.; Darbre, T. Org. Biomol. Chem. 2005, 3, 1850.
15. Wong, C.-H.; Machajewski, T. D. Angew. Chem., Int. Ed. 2000, 39,
1352.
´
´
Casas, J.; Sunden, H.; Cordova, A. Tetrahedron 2006, 62, 357; (l) Chi,
Y.; Gellman, S. J. Am. Chem. Soc. 2006, 128, 6804; (m) Rodriguez, B.;
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Bolm, C. J. Org. Chem. 2006, 71, 2888; (n) Cordova, A. Synlett 2003,
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1651; (o) Cordova, A. Chem. Eur. J. 2004, 10, 1987; (p) Ibrahem, I.;
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16. For references on the removal of the PMP group see: (a) Verkade, J.
M. M.; Van Hemert, L. J. C.; Quaedflieg, P. J. L. M.; Schoemaker, H.
Cordova, A. Tetrahedron Lett. 2005, 46, 2839; (q) Liao, W.-W.;
´
Ibrahem, I.; Cordova, A. Chem. Commun. 2006, 674; (r) Hayashi, Y.;
E.; Schurmann, M.; van Delft, F. L.; Rutjes, F. P. J. T. Adv. Synth.
¨
Tsuboi, W.; Ashimine, I.; Urushima, T.; Shoji, M.; Sakai, K. Angew.
Chem., Int. Ed. 2003, 42, 3677; (s) Hayashi, Y.; Urushima, T.; Shoji,
M.; Uchimary, T.; Shiina, I. Adv. Synth. Catal. 2005, 347, 1595.
8. For selected anti-selective Mannich reactions see: (a) Kano, T.;
Yamaguchi, Y.; Tokuda, O.; Maruoka, K. J. Am. Chem. Soc. 2005,
127, 16408; (b) Mitsumori, S.; Zhang, H.; Cheong, P. H.-Y.; Houk,
K. N.; Tanaka, F.; Barbas, C. F., III. J. Am. Chem Soc. 2006, 128,
Catal. 2007, 349, 1332; and references cited therein; (b) Verkade, J. M.
M.; Van Hemert, L. J. C.; Quaedflieg, P. J. L. M.; Alsters, P. L.; van
Delft, F. L.; Rutjes, F. P. J. Tetrahedron Lett. 2006, 47, 8109.
17. Typical experimental procedure for the Mannich reactions with
DHA. To a stirred solution of aldehyde 3 (0.25 mmol), acetic acid
(0.023 mmol) and p-methoxyanisidine
2 (0.225 mmol) in NMP
(0.5 mL) were added catalyst 8 (20 mol %) and the dimer of DHA 1
(0.25 mmol). The reaction mixture was stirred at +4 °C for 72 h. The
crude reaction mixture was purified by column chromatography
(pentane–EtOAc mixtures) to afford the corresponding dihydroxy-b-
amino ketones 4. anti-4a: Yellow oil: 1H NMR (400 MHz, CDCl3):
d = 8.16 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 6.72 (d,
J = 8.4 Hz, 2H), 6.57 (d, J = 8.4 Hz, 2H), 4.89 (d, J = 4.4 Hz, 1H),
4.81 (d, J = 4.0 Hz, 1H), 4.45 (d, J = 20 Hz, 1H), 4.15 (d, J = 20 Hz,
1H), 3.70 (s, 3H) 13C NMR (100 MHz, CDCl3): d = 210.1, 153.6,
148.0, 145.2, 139.2, 128.9, 124.1, 116.3, 115.2, 77.3, 67.4, 61.0, 55.9;
HRMS (ESI): calcd for [M+Na] (C17H18N2O6) requires m/z
´
1040; (c) Cordova, A.; Barbas, C. F., III. Tetrahedron Lett. 2002, 43,
7749; (d) Franzen, J.; Marigo, M.; Fielenbach, D.; Wabnitz, T. C.;
Kjaersgaard, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2005, 127,
´
18296; (e) Ibrahem, I.; Cordova, A. Chem. Commun. 2006, 1760; (f)
Kano, T.; Hato, Y.; Maruoka, K. Tetrahedron Lett. 2006, 47, 8467;
(g) Zhang, H.; Mifsud, M.; Tanaka, F.; Barbas, C. F., III. J. Am.
Chem. Soc. 2006, 128, 9630.
´
9. (a) Ibrahem, I.; Zou, W.; Engqvist, M.; Xu, Y.; Cordova, A. Chem.
Eur. J. 2005, 11, 7024; (b) Ramasastry, S. S. V.; Zhang, Z.; Tanaka,
F., ; Barbas, C. F., III. J. Am. Chem. Soc. 2007, 129, 288; (c) Dziedzic,
23
´
P.; Cordova, A. Tetrahedron: Asymmetry 2007, 18, 1033; (d) Cheng,
369.1057; found, 369.1049, ½aꢀD ꢁ25.0 (c = 1, CHCl3). The enantio-
L.; Han, X.; Huang, H.; Wah Wong, M.; Lu, Y. Chem. Commun.
2007, 4143; (e) Cheng, L.; Wu, X.; Lu, X. Org. Biomol. Chem. 2007, 5,
1018.
meric excess was determined by HPLC with an OD-H column
(n-hexane–i-PrOH = 88:12, k = 254 nm), 1.0 mL/min; anti-diastereo-
mer:major enantiomer tr = 63.9 min, minor enantiomer = 83.7 min.
syn-4a0: Yellow oil. 1H NMR (400 MHz, CDCl3): d = 8.16 (d,
J = 8.70 Hz, 2H), 7.52 (d, J = 8.70 Hz, 2H), 6.47 (d, J = 8.80 Hz,
2H), 5.00 (d, J = 2.04 Hz, 1H), 4.60 (d, J = 2.34 Hz, 1H), 4.55 (s, 2H),
4.43 (d, J = 19.91 Hz, 1H), 4.11 (d, J = 19.98, 1H), 3.67 (s, 3H); 13C
NMR (100 MHz, CDCl3): 209.4, 153.7, 141.7, 139.2, 129.4, 128.2,
126.1, 115.6, 114.9, 78.3, 66.2, 60.0, 55.7; [a]D ꢁ4.5 (c = 0.5, CHCl3).
HRMS (ESI): calcd for [M+H]+ (C17H18N2NaO6) requires m/z
369.1057; found, 369.1049. The enantiomeric excess was determined
by HPLC with an OD-H column (n-hexane–i-PrOH = 88:12, k =
254 nm), 1.0 mL/min; syn-diastereomer:major enantiomer tr =
47.5 min, minor enantiomer = 55.7 min.
10. (a) Enders, D.; Grondal, C.; Vrettou, M.; Raabe, G. Angew. Chem.,
Int. Ed. 2005, 44, 4079; (b) Enders, D.; Grondal, C.; Vrettou, M.
Synthesis 2006, 3597; (c) Enders, D.; Vrettou, M. Synthesis 2006,
2155.
11. Westermann, B.; Neuhaus, C. Angew. Chem., Int. Ed. 2005, 44, 4077.
´
12. (a) Ibrahem, I.; Cordova, A. Tetrahedron Lett. 2005, 46, 3363; (b)
Ibrahem, I.; Zou, W.; Xu, Y.; Co´rdova, A. Adv. Synth. Catal. 2006,
348, 211; (c) See also Ref. 9a.
13. For an excellent review on the use of protected dihydroxyacetone in
synthesis see: (a) Enders, D.; Voith, M.; Lenzen, A. Angew. Chem.,
Int. Ed. 2005, 44, 1330; For reviews on the use of amino acids in sugar