8502
P. Szolcsaꢀnyi, T. Gracza / Tetrahedron 62 (2006) 8498–8502
3.25 (br d, 1H, J5,6¼3.0 Hz, H-5), 3.55 (d, 1H, J¼13.5 Hz,
NCH2Ph), 3.62 (d, 1H, J¼13.5 Hz, NCH2Ph), 3.65 (t, 1H,
Acknowledgements
0
ꢀ
ꢀ
J2,3¼5.1 Hz, H-2), 3.78 (dd, 1H, J6,5¼3.6, J6,6 ¼9.3 Hz,
We are grateful to Dr. Nad’a Pronayova for NMR service
H-6), 4.02 (d, 1H, J6 ,6¼9.0 Hz, H-60), 4.18 (d, 1H, J3,2
¼
and Dr. Katarına Hrobonova for HPLC analyses. This
work was supported by Science and Technology Assistance
Agency under the contract no. APVT-20-000904 and Slovak
National R&D Programme no. 2003SP200280203.
0
´
ˇ
ꢀ
5.1 Hz, H-3), 4.44 (d, 1H, J¼12.3 Hz, OCH2Ph), 4.51 (d,
1H, J4,5¼1.2 Hz, H-4), 4.55 (d, 1H, J¼12.3 Hz, OCH2Ph),
7.25–7.36 (m, 10H, 2ꢁPh); dC (75 MHz, CDCl3) 48.3 (t,
C-1), 59.3 (t, NCH2Ph), 63.9 (t, C-6), 64.0 (d, C-5), 71.5
(t, OCH2Ph), 73.1 (d, C-4), 76.4 (d, C-2), 80.3 (d, C-3),
127.3, 127.6, 127.7, 128.0, 128.4, 128.9 (all d, all CH-Ph),
137.9, 138.2 (2ꢁs, 2ꢁCq-Ph); IR: nmax (KBr)/cmꢂ1 697,
739, 746, 891, 1029, 1049, 1057, 1114, 1133, 1454, 2804,
2883, 2951, 3395; m/z (MALDI) 323 [MꢂH-1]+; found C
73.79, H 7.14, N 4.32%; C20H23NO3 requires C 73.62, H
7.22, N 4.30%.
References and notes
€
1. Stutz, A. E. Iminosugars as Glycosidase Inhibitors, Nojiri-
mycin and Beyond; Wiley-VCH: Weinheim, Germany, 1999.
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Depezay, J.-C. Bioorg. Med. Chem. Lett. 1996, 6, 1667–1672.
4.1.3. Typical procedure for the catalytic debenzylation
of 2 or 10. Protected piperidine 2 or 10 (87 mg,
0.193 mmol) was dissolved in EtOH (8 ml), 10% Pd–C
(55 mg) was added followed by 35% aq HCl (10 drops)
and the resulting black suspension was stirred under hydro-
gen atmosphere (balloon) at 23 ꢀC over 12 h. The reaction
mixture was filtered, solids were washed with EtOH
(2ꢁ5 ml) and the clear filtrate was co-evaporated with
AcOEt (5 ml) in vacuo yielding 12 or 13 (42 mg, 100%) as
a pale-yellow hygroscopic foam.
ꢀ
7. (a) Szolcsanyi, P.; Gracza, T.; Koman, M.; Pronayova, N.;
Liptaj, T. Chem. Commun. 2000, 471–472; (b) Szolcsanyi, P.;
ꢀ
ꢀ
ꢀ
ꢀ
Gracza, T.; Koman, M.; Pronayova, N.; Liptaj, T. Tetrahedron:
Asymmetry 2000, 11, 2579–2597.
ꢀ
Data for 6-chloro-1,5,6-trideoxy-1,5-imino-L-iditol hydro-
chloride 12: [a]2D4 +18 (c 0.26, EtOH); dH (600 MHz,
8. Wada, M.; Aiura, H.; Akiba, K. Heterocycles 1987, 26, 929–934.
9. (a) Martin, O. R.; Liu, L.; Yang, F. Tetrahedron Lett. 1996, 11,
2579–2597; (b) H€ugel, H. M.; Hughes, A. B.; Khalil, K. Aust. J.
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2003, 14, 1969–1972.
10. Bernotas, R. C. Tetrahedron Lett. 1990, 31, 469–472.
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J. Chem. 1988, 41, 813–815.
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2727–2740.
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123–133.
0
CD3OD) 3.31 (ddd, 1H, J1,3¼1.1, J1,2¼2.2, J1,1 ¼13.2 Hz,
H-1), 3.48 (dd, 1H, J1 ,2¼1.9, J1 ,1¼13.2 Hz, H-10), 3.70
0
0
0
(dtd, 1H, J5,4¼1.5, J5,6 ¼5.8, J5,6¼8.5 Hz, H-5), 3.90 (ddd,
0
1H, J6,4¼0.6, J6,5¼8.7, J6,6 ¼12.0 Hz, H-6), 3.97 (dd, 1H,
J6 ,5¼5.7, J6 ,6¼12.0 Hz, H-60), 3.99 (m, 1H, J2,1 ¼1.9, J2,1
¼
0
0
0
2.1, J2,3¼3.1 Hz, H-2), 4.00 (dd, 1H, J4,5¼1.1, J4,3¼3.5 Hz,
H-4), 4.01 (m, 1H, J3,2¼3.2, J3,4¼3.7 Hz, H-3); dC
(125 MHz, CD3OD) 42.3 (t, C-6), 47.5 (t, C-1), 58.1 (d,
C-5), 67.7 (d, C-4), 67.9 (d, C-2), 69.5 (d, C-3); nmax (film
on KBr)/cmꢂ1 756, 1002, 1054, 1131, 1560, 2437, 2534,
3014, 3273, 3421; found C 33.21, H 5.88, Cl 32.45, N
6.33%; C6H13Cl2NO3 requires C 33.05, H 6.01, Cl 32.51,
N 6.42%.
14. Limousin, C.; Olesker, A.; Cleophax, J.; Petit, A.; Loupy, A.;
Lukacs, G. Carbohydr. Res. 1998, 312, 23–32.
Data for 6-chloro-1,5,6-trideoxy-1,5-imino-L-altritol hydro-
chloride 13: [a]2D4 ꢂ19 (c 0.27, EtOH); dH (600 MHz,
15. Fenton, D. M.; Steinwand, P. J. J. Org. Chem. 1974, 39, 701–
704; Hosokawa, T.; Uno, T.; Inui, S.; Murahashi, S.-I. J. Am.
Chem. Soc. 1981, 103, 2318–2323; Karandin, A.; Gusevskaya,
E. V.; Likhobolov, V. A.; Stepanov, A. G.; Talzi, E. P. Kinet.
Catal. 1990, 31, 506–510; Zargarian, D.; Alper, H. Organo-
metallics 1991, 10, 2914–2921; Fairlamb, I. J. S.; Lee, A. F.;
0
CD3OD) 3.18 (dd, 1H, J1,2¼2.5, J1,1 ¼12.9 Hz, H-1), 3.42
(dd, 1H, J1 ,2¼1.4, J1 ,1¼13.0 Hz, H-10), 3.57 (dtd, 1H, J5,6
¼
0
0
0
2.9, J5,6¼7.6, J5,4¼10.4 Hz, H-5), 3.95 (dd, 1H, J6,5¼7.6,
0
J6,6 ¼12.6 Hz, H-6), 3.96 (t, 1H, J3,4¼3.2, J3,2¼3.8 Hz,
€
H-3), 4.00 (dd, 1H, J4,3¼2.9, J4,5¼10.4 Hz, H-4), 4.05 (m,
Loe-Mie, F. E. M.; Niemela, E. H.; O’Brien, C. T.; Whitwood,
0
1H, J2,1¼2.2, J2,3¼4.2 Hz, H-2), 4.12 (dd, 1H, J6 ,5¼2.9,
A. C. Tetrahedron 2005, 61, 9827–9838; Batsanov, A. S.;
Collings, J. C.; Fairlamb, I. J. S.; Holland, J. P.; Howard,
J. A. K.; Lin, Z.; Marder, T. B.; Parsons, A. C.; Ward, R. M.;
Zhu, J. J. Org. Chem. 2005, 70, 703–706.
J6 ,6¼12.6 Hz, H-60); dC (125 MHz, CD3OD) 43.4 (t, C-6),
0
46.4 (t, C-1), 57.5 (d, C-5), 66.1 (d, C-4), 67.7 (d, C-2),
70.4 (d, C-3); nmax (film on KBr)/cmꢂ1 756, 881, 1071,
1434, 2517, 3346; found C 32.88, H 6.05, Cl 32.60, N
6.40%; C6H13Cl2NO3 requires C 33.05, H 6.01, Cl 32.51,
N 6.42%.
ꢀ
16. Szolcsanyi, P.; Gracza, T. Chem. Commun. 2005, 3948–3950.
17. Takahata, H.; Banba, Y.; Ouchi, H.; Nemoto, H. Org. Lett.
2003, 5, 2527–2529.