A. Dondoni et al. / Tetrahedron 57 *2001) 7719±7727
7723
1125, 1080, 1040, 1020 cm21
.
13H NMR *300 MHz,
1H, J2,33.0 Hz, H-2), 4.72 and 4.62 *2d, 2H, J11.6 Hz,
PhCH2), 4.72 and 4.60 *2d, 2H, J12.0 Hz, PhCH2), 4.08
*dd, 1H, J3,49.2, J4,58.5 Hz, H-4), 3.89 *dd, 1H, H-3),
3.86±3.77 *m, 3H, H-5, 2H-6). 13C NMR *CDCl3):
d168.8, 142.3, and 120.5 *Th), 138.3, 138.2, and 128.2±
127.4 *Ph), 79.6 *C-3), 75.0 *C-1, C-2, C-5), 74.8 *PhCH2),
74.5 *C-4), 73.3, 72.4, and 71.8 *PhCH2), 69.3 *C-6).
MALDI-TOF MS *607.8): 608.9 *M1H). Anal. Calcd for
C37H37NO5S: C, 73.12; H, 6.14; N, 2.30. Found: C, 73.40;
H, 6.19; N, 2.46.
CDCl3): d7.81 and 7.39 *2d, 2H, J3.2 Hz, Th), 7.38±
7.22 and 7.12±7.07 *2m, 15H, 3Ph), 5.50 *d, 1H,
J1,23.2 Hz, H-1), 4.63 and 4.53 *2d, 2H, J12.1 Hz,
PhCH2), 4.54 and 4.42 *2d, 2H, J11.8 Hz, PhCH2), 4.48
*ddd, 1H, J3,48.2, J4,5a2.6, J4,5b3.6 Hz, H-4), 4.33 *dd,
1H, J2,34.0 Hz, H-2), 4.29 *dd, 1H, H-3), 4.21 *s, 2H,
PhCH2), 3.83 *dd, 1H, J5a,5b11.0 Hz, H-5a), 3.64 *dd,
1H, H-5b). 13C NMR *CDCl3): d169.7, 142.0, and 119.8
*Th), 138.2, 137.7, 137.6, and 128.4±127.6 *Ph), 81.1 *C-1),
80.2 *C-4), 79.5 *C-3), 78.6 *C-2), 73.5, 73.2, and 72.6
*PhCH2), 69.4 *C-5). MALDI-TOF MS *487.6): 488.7
*M1H). Anal. Calcd for C29H29NO4S: C, 71.43; H, 5.99;
N, 2.87. Found: C, 71.62; H, 6.10; N, 3.03.
Eluted second was the known1 C-glycoside b-3e *19%) as a
syrup; [a]D219.2 *c1.0, CHCl3), lit.1 [a]D219.8
1
*c1.0, CHCl3). H NMR *300 MHz, CDCl3): d7.75 *d,
1H, J3.2 Hz, Th), 7.42±6.95 *m, 21H, 4Ph, Th), 4.86 *d,
1H, J1,20.9 Hz, H-1), 4.77 and 4.65 *2d, 2H, J11.5 Hz,
PhCH2), 4.93 and 4.62 *2d, 2H, J11.0 Hz, PhCH2), 4.75
and 4.64 *2d, 2H, J12.0 Hz, PhCH2), 4.61 and 4.27 *2d,
2H, J11.5 Hz, PhCH2), 4.42 *dd, 1H, J2,32.9 Hz, H-2),
4.05 *dd, 1H, J3,49.5, J4,59.5 Hz, H-4), 3.85 *d, 2H,
J5,63.6 Hz, 2H-6), 3.82 *dd, 1H, H-3), 3.70 *dt, 1H,
H-5). 13C NMR *CDCl3): d169.5, 142.0, and 119.4 *Th),
138.6±138.2 and 128.5±127.3 *Ph), 83.7 *C-3), 80.4 *C-5),
78.5 *C-1), 76.5 *C-2), 75.2 *PhCH2), 74.6 *C-4, PhCH2),
71.9 and 73.6 *PhCH2), 69.4 *C-6). MALDI-TOF MS
*607.8): 609.0 *M1H).
1.1.4. 2-*2,3,4,6-Tetra-O-benzyl-d-glucopyranosyl)thia-
zole *3d). Thiazolylketose acetate 2d was treated with
SmI2 as described for the preparation of a-3a to give,
after the same workup, a 2:1 a,b mixture of the known1
C-glycosides 3d. Analytical samples were obtained by
column chromatography *30:1 toluene±acetone). Eluted
®rst was a-3d as a syrup; [a]D138.4 *c1.0, CHCl3),
lit.1 [a]D138.3 *c1.0, CHCl3). 1H NMR *300 MHz,
CDCl3): d7.85 *d, 1H, J3.1 Hz, Th), 7.40±7.05 *m,
21H, 4Ph, Th), 5.29 *d, 1H, J1,26.0 Hz, H-1), 4.95 and
4.80 *2d, 2H, J11.3 Hz, PhCH2), 4.81 and 4.50 *2d, 2H,
J10.7 Hz, PhCH2), 4.76 and 4.68 *2d, 2H, J12.0 Hz,
PhCH2), 4.62 and 4.47 *2d, 2H, J12.0 Hz, PhCH2), 4.30
*dd, 1H, J2,38.7, J3,48.7 Hz, H-3), 4.03 *dd, 1H, H-2),
3.96 *ddd, 1H, J4,510.0, J5,6a3.3, J5,6b2.0 Hz, H-5),
3.79 *dd, 1H, H-4), 3.73 *dd, 1H, J6a,6b10.6 Hz, H-6a),
3.66 *dd, 1H, H-6b). 13C NMR *CDCl3): d165.8, 142.8,
and 120.2 *Th), 138.8, 138.4, 138.1, 137.9, and 128.5±127.8
*Ph), 82.1 *C-3), 79.6 *C-2), 77.8 *C-4), 75.3, 75.0, and 73.7
*PhCH2), 73.6 *C-5, PhCH2), 73.2 *C-1), 68.7 *C-6).
MALDI-TOF MS *607.8): 608.7 *M1H).
1.1.6.
2-*2,3,4,6-Tetra-O-benzyl-d-galactopyranosyl)-
thiazole *3f). Thiazolylketose acetate 2f was treated with
SmI2 as described for the preparation of a-3a to give, after
column chromatography *from 6:1 to 4:1 cyclohexane±
AcOEt), ®rst a-3f *50%) as a syrup; [a]D140.0 *c1.0,
CHCl3). IR: 2990, 2930, 2870, 1605, 1490, 1450, 1370,
1355, 1315, 1090, 1025, 910, 880 cm21
.
1H NMR
*300 MHz, CDCl3): d7.81 and 7.36 *2d, 2H, J3.2 Hz,
Th), 7.35±7.25 and 7.11±7.07 *2m, 20H, 4Ph), 5.32 *d, 1H,
J1,23.3 Hz, H-1), 4.65 and 4.57 *2d, 2H, J11.9 Hz,
PhCH2), 4.64 *s, 2H, PhCH2), 4.57 and 4.52 *2d, 2H,
J12.2 Hz, PhCH2), 4.49 *ddd, 1H, J4,52.8, J5,6a8.0,
J5,6b3.7 Hz, H-5), 4.39 and 4.35 *2d, 2H, J11.5 Hz,
PhCH2), 4.18 *dd, 1H, J2,35.8 Hz, H-2), 4.16 *dd, 1H,
H-4), 4.04 *dd, 1H, J6a,6b11.3 Hz, H-6a), 3.95 *dd, 1H,
H-3), 3.79 *dd, 1H, H-6b). 13C NMR *CDCl3): d168.6,
142.0, and 119.4 *Th), 138.2, 137.7, and 128.2±127.5
*Ph), 77.1 *C-2), 75.5 *C-3), 74.8 *C-5), 73.6 *C-4,
PhCH2), 73.0, 72.9, and 72.4 *PhCH2), 70.6 *C-1), 66.2
*C-6). MALDI-TOF MS *607.8): 608.8 *M1H). Anal.
Calcd for C37H37NO5S: C, 73.12; H, 6.14; N, 2.30. Found:
C, 73.00; H, 6.21; N, 2.48.
Eluted second was b-3d as a white solid; mp112±113 8C
*AcOEt±hexane), lit1 mp112±113 8C *AcOEt±hexane);
[a]D110.6 *c1.0, CHCl3), lit.1 [a]D110.4 *c1.0,
1
CHCl3). H NMR *300 MHz, CDCl3): d7.84 and 7.40
*2d, 2H, J3.1 Hz, Th), 7.40±7.00 *m, 20H, 4Ph), 4.95
and 4.89 *2d, 2H, J10.8 Hz, PhCH2), 4.86 and 4.60 *2d,
2H, J10.8 Hz, PhCH2), 4.74±4.67 *m, 1H, H-1), 4.62 and
4.56 *2d, 2H, J11.5 Hz, PhCH2), 4.52 and 4.15 *2d, 2H,
J10.1 Hz, PhCH2), 3.88±3.70 *m, 5H, H-2, H-3, H-4, 2H-
6), 3.65 *ddd, 1H, J4,59.0, J5,6aJ5,6b3.1 Hz, H-5). 13C
NMR *CDCl3): d167.6, 142.5, and 119.9 *Th), 138.5,
138.2, 137.9, 137.7, and 128.4±127.6 *Ph), 86.4, 83.1, and
77.9 *C-2, C-3, C-4), 79.7 *C-5), 78.3 *C-1), 75.6, 75.1,
74.9, and 73.4 *PhCH2), 68.9 *C-6). MALDI-TOF MS
*607.8): 608.8 *M1H).
Eluted second was the known1 C-glycoside b-3f *36%) as a
syrup; [a]D0.0 *c1.0, CHCl3), lit.1 [a]D0 *c1.0,
CHCl3). 1H NMR *300 MHz, CDCl3): d7.80 *d, 1H,
J3.2 Hz, Th), 7.40±7.20 *m, 21H, 4Ph, Th), 5.01 and
4.67 *2d, 2H, J11.8 Hz, PhCH2), 4.78 and 4.73 *2d, 2H,
J10.6 Hz, PhCH2), 4.66 *d, 1H, J1,29.4 Hz, H-1), 4.66
and 4.28 *2d, 2H, J10.6 Hz, PhCH2), 4.47 and 4.41 *2d,
2H, J11.8 Hz, PhCH2), 4.24 *dd, 1H, J2,39.4 Hz, H-2),
4.05 *dd, 1H, J3,42.9, J4,5,0.6 Hz, H-4), 3.75 *dt, 1H,
J5,66.5 Hz, H-5), 3.73 *dd, 1H, H-3), 3.63 *d, 2H, 2H-6).
13C NMR *CDCl3): d167.9, 142.5, and 119.8 *Th), 138.9±
137.9 and 128.4±127.5 *Ph), 79.4 *C-2), 78.7 *C-1), 84.0
and 77.7 *C-3, C-5), 75.0, 74.4, 73.4, and 72.5 *PhCH2),
1.1.5.
2-*2,3,4,6-Tetra-O-benzyl-d-mannopyranosyl)-
thiazole *3e). Thiazolylketose acetate 2e was treated with
SmI2 as described for the preparation of a-3a to give, after
column chromatography *from 6:1 to 3:1 cyclohexane±
AcOEt), ®rst a-3e *75%) as a syrup; [a]D145.0 *c0.9,
CHCl3). IR: 2930, 2870, 1605, 1450, 1365, 1090,
1
1025 cm21. H NMR *300 MHz, CDCl3): d7.71 *d, 1H,
J3.2 Hz, Th), 7.46±7.24 and 7.17±7.12 *2m, 21H, Th,
4Ph), 5.41 *d, 1H, J1,22.6 Hz, H-1), 4.86 and 4.52 *2d,
2H, J10.9 Hz, PhCH2), 4.80 *s, 2H, PhCH2), 4.77 *dd,