C. B. Davis et al. / Carbohydrate Research 342 (2007) 1773–1780
1779
decyl chain), 14.5 (2 · CH3); LRMS (ESI) m/z 457
[(M+Na)+ 100%]; HRMS calcd for C23H46NaO5S:
457.2964; found, 457.2959. Anal. Calcd for C23H46O5S-
ÆMeOH: C, 61.76; H, 10.80. Found: C, 61.69; H, 10.89.
J3,2 = 4.1 Hz, H-3), 5.01 (d, 1H, J1,2 = 3.7 Hz, H-1),
4.62 (dd, 1H, J4,5 = 3.8, J4,3 = 7.4 Hz, H-4), 4.32 (dd,
0
1H, J6,6 = 11.7, J6,5 = 5.2 Hz, H-6), 4.14 (dd, 1H,
J6 ,6 = 11.7, J6 ,5 = 6.9 Hz, H-60), 3.10 [m, 1H,
S(O)2CH], 2.13, 2.10, 2.09, 2.05 (4 · s, 4 · 3H,
4 · OCOCH3), 1.60–2.05 (m, 4H, 2 · CH2, heptadecyl
chain), 1.19–1.55 (m, 24H, 12 · CH2, heptadecyl chain),
0.87 (m, 6H, 2 · CH3); 13C NMR (CDCl3) b-anomer: d
170.3, 170.1, 169.8, 169.0 (4 · OCOCH3), 91.5 (C-1),
81.8 (C-4), 76.1 (C-3), 75.6 (C-2), 68.4 (C-5), 61.9 (C-
6), 60.1 (S(O)2CH), 31.8, 29.6, 29.5, 29.3, 29.2, 28.1,
26.7, 26.6, 26.3, 22.6 (14 · CH2, heptadecyl chain),
20.7, 20.7, 20.6 (4 · OCOCH3), 14.1 (2 · CH3); LRMS
(ESI) m/z 657 [(M+Na)+ 100%]. Anal. Calcd for C31
H54O11S: C, 58.65; H, 8.57. Found: C, 58.85; H, 8.75.
0
0
3.7. 9-Heptadecyl S,S-dioxo-(2,3,5,6-tetra-O-acetyl)-1-
thio-b-D-galactofuranoside (15)
3.7.1. 9-Heptadecyl 2,3,5,6-tetra-O-acetyl-1-thio-b-D-
galactofuranoside (14b). To a solution of 1,2,3,5,6-
penta-O-acetyl-D-galactofuranose14
(13b)
(1.49 g,
3.82 mmol) in dry CH2Cl2 (40 mL) was added BF3ÆOEt2
(580 lL, 4.58 mmol, 1.2 M equiv) and the solution was
stirred for 10 min at 0 ꢁC under N2. 9-Heptadecanethiol
(12) (1.04 g, 3.82 mmol) was then added and the reaction
mixture stirred for 3 h at rt under N2. After this time the
solvent was removed under reduced pressure. The resi-
due was then diluted in CH2Cl2 (50 mL) and extracted
with satd aq NaHCO3 (100 mL), dried over MgSO4, fil-
tered, and the solvent removed under reduced pressure.
The residue was purified by chromatography (hexane–
EtOAc, 4:1) to furnish 14b (a/b ꢀ 1:9 by 1H NMR anal-
ysis) as a clear syrup (1.93 g, 84%). Rf = 0.59 (hexane–
3.8. 9-Heptadecyl S,S-dioxo-1-thio-b-D-galactofuranoside
(4)
To a solution of 9-heptadecyl S,S-dioxo-(2,3,5,6-tetra-
O-acetyl)-1-thio-b-D-galactofuranoside (15) (230 mg,
0.36 mmol) in MeOH (20 mL) was added K2CO3 solu-
tion (5 equiv, 250 mg, 1.8 mmol, dissolved in 0.5 mL
water). The reaction mixture was stirred for 15 min at
rt. After this time the reaction mixture was filtered
through Celite, and the filtrate evaporated under re-
duced pressure. The residue was purified by chromato-
graphy (EtOAc) to furnish 4 as a white amorphous solid
1
EtOAc, 4:1); H NMR (CDCl3) b-anomer: d 5.41 (m,
1H, H-5), 5.32 (m, 1H, H-1), 5.08 (app t, 1H,
J2,3ꢂ2,1 = 2.4 Hz, H-2), 5.01 (dd, 1H, J3,2 = 2.1,
J3,4 = 6.0 Hz, H-3), 4.39 (dd, 1H, J4,5 = 3.3,
J4,3 = 6.0 Hz, H-4), 4.31 (dd, 1H, J6,5 = 4.5,
1
0
0
J6,6 = 12.0 Hz, H-6), 4.18 (dd, 1H, J6 ,5 = 7.2,
0
(162 mg, 96%). Rf = 0.59 (EtOAc); H NMR (CD3OD)
J6 ,6 = 11.7 Hz, H-60), 2.78 (m, 1H, SCHR2), 2.14,
b-anomer: d 4.82 (d, 1H, J1,2 = 5.3 Hz, H-1), 4.64 (dd,
1H, J2,3 = 6.2, J2,1 = 5.3 Hz, H-2), 4.18 (dd, 1H,
J3,4 = 8.8, J3,2 = 6.2 Hz, H-3), 4.04 (dd, 1H, J4,5 = 2.6,
J4,3 = 8.8 Hz, H-4), 3.69 (m, 1H, H-5), 3.59 (m, 2H,
H-6 and H-60), 3.19 (m, 1H, CH), 1.60–2.01 (m, 4H,
SCH(CH2)2), 1.24–1.60 (m, 24H, 12 · CH2), 0.90 (app
t, 6H, J = 6.4, J = 7.0 Hz, 2 · CH3); 13C NMR
(CD3OD) b-anomer: d 94.5 (C-1), 84.8 (C-4), 77.9 (C-
3), 77.5 (C-2), 71.4 (C-5), 64.4 (C-6), 60.6 [S(O)2CHR2],
33.0, 30.7, 30.6, 30.4, 30.4, 28.8, 27.6, 27.5, 27.3, 23.8
(14 · CH2), 14.5 (2 · CH3); LRMS (ESI) m/z 489
[(M+Na)+ 100%]; HRMS calcd for C23H46NaO7S:
489.2862; found, 489.2855.
2.11, 2.10, 2.05 (4 · s, 4 · 3H, 4 · OCOCH3), 1.21–1.65
(m, 28H, 14 · CH2, heptadecyl chain), 0.89 (m, 6H,
2 · CH3); a-anomer: 5.33 (H-1 a, overlapped by H-1
b); 13C NMR (CDCl3) b-anomer: d 170.5, 170.0, 169.7
(4 · OCOCH3), 87.4 (C-1), 82.2 (C-2), 79.1 (C-4), 76.6
(C-3), 69.1 (C-5), 62.7 (C-6), 46.7 (SCHR2), 35.3, 34.7,
31.9, 29.6, 29.5, 29.3, 26.8, 26.7, 22.7 (14 · CH2, hepta-
decyl chain), 20.8, 20.7 (4 · OCOCH3), 14.1 (2 · CH3);
LRMS (ESI) m/z 625 [(M+Na)+ 100%].
3.7.2. 9-Heptadecyl S,S-dioxo-(2,3,5,6-tetra-O-acetyl)-1-
thio-b-D-galactofuranoside (15). To a solution of 9-hep-
tadecyl 2,3,5,6-tetra-O-acetyl-1-thio-b-D-galactofurano-
side (14b) (401 mg, 0.67 mmol) in dry CH2Cl2 (20 mL)
was added m-CPBA (3 M equiv, 345 mg, 2.00 mmol)
and the solution was refluxed for 2 h. After this time
the mixture was diluted to 80 mL with CH2Cl2 and
quenched with satd aq NaHCO3 (80 mL). The organic
layer was separated and dried (Na2SO4), filtered, and
the solvent evaporated under reduced pressure. The resi-
due was purified by chromatography (hexane–EtOAc,
3:1) to furnish 15 as a clear syrup (336 mg, 80%).
Rf = 0.3 (hexane–EtOAc, 3:1); IR (neat): m 2930, 2857,
Acknowledgments
We gratefully acknowledge the financial support of the
Australian Research Council (ARC), the National
Health and Medical Research Council of Australia
(NHMRC), Glykoz Pty Ltd, and Griffith University
for the award of a Postgraduate Research Scholarship
and the Institute for Glycomics, Griffith University, for
an Institute Postgraduate Award to C.D. M.vI. grate-
fully acknowledges the support of the ARC for the award
of a Federation Fellowship. Micromyx LLC, Kalama-
zoo, MI, USA, are thanked for performing the bioassays.
1
1754, 1373, 1310, 1228, 1051 cmꢁ1; H NMR (CDCl3)
b-anomer: d 5.96 (app t, 1H, J1,2ꢂ2,3 = 3.9 Hz, H-2),
5.27 (m, 1H, H-5), 5.22 (dd, 1H, J3,4 = 7.4,