F. Compostella, D. Colombo, P. Ferraboschi, A. Scala, L. Toma, F. Ronchetti
(m, 2 H, OCH2CH2), 3.43 (dd, J ϭ 10.5 Hz, J ϭ 7.0 Hz, 1 H,
H), 5.04 (dd, J4,5 ϭ 9.5 Hz, J3,4 ϭ 9.5 Hz, 1 H, 4-H), 5.16 (dd, 1
FULL PAPER
CHaHbCHCHaHb), 3.51 (dd, J ϭ 10.5 Hz, J ϭ 6.0 Hz, 1 H, H, 3-H), 7.18Ϫ7.36 (m, 5 H, Ph). 13C NMR: δ ϭ 14.7, 21.2Ϫ21.4
CHaHbCHCHaHb), 3.58 (dd, J ϭ 3.5 Hz, 1 H, CHaHbCHCHaHb), (COCH3), 23.3, 25.8, 29.9, 30.2, 30.3, 32.5, 32.8, 62.8, 69.2, 72.4 (2
3.62 (dd, J ϭ 4.5 Hz, 1 H, CHaHbCHCHaHb), 3.84 (m, 1 H, 5-H), C), 73.5, 73.7, 74.0, 81.5, 101.9, 128.2Ϫ140.0 (C6H5), 170.0Ϫ171.3
3.96 (m, 1 H, CH2CHCH2), 4.10 (m, 2 H, 2 ϫ 6-H), 4.51 (s, 2 H, (COCH3). MS: m/z ϭ 612 [M ϩ NH4]ϩ. C31H46O11 (594.7): calcd.
OCH2Ph), 4.72 (d, J1,2 ϭ 8.0 Hz, 1 H, 1-H), 4.98 (dd, J3,4 ϭ 3.5 Hz,
1 H, 3-H), 5.17 (dd, J2,3 ϭ 10.5 Hz, 1 H, 2-H), 5.35 (br. d, 1 H, 4-
H), 7.20Ϫ7.36 (m, 5 H, Ph). 13C NMR: δ ϭ 14.7, 21.3, 23.3, 26.5,
30.3, 32.6, 62.0, 67.8, 69.8, 70.8, 71.3, 71.7, 72.2, 72.4, 74.0, 79.0,
102.0, 128.3, 129.0, 170.0, 171.0. MS: m/z ϭ 614 [M ϩ NH4]ϩ.
C30H44O12 (596.7): calcd. C 60.39, H 7.43; found C 60.61, H 7.15.
C 62.61, H 7.80; found C 62.85, H 7.70.
3-O-Benzyl-2-O-β- -galactopyranosyl-1-O-hexyl-sn-glycerol (17):
D
Sodium methoxide (0.8 solution in MeOH, 2.3 mL) was added
to a solution of 13 (0.37 g, 0.62 mmol) in methanol (8 mL). After
2 h at room temperature, the reaction mixture was neutralized with
Dowex 50 ϫ 8 (Hϩ form) and then filtered. The solvent was re-
moved under reduced pressure, to afford pure 17 (0.26 g, quant) as
(2R)-1-O-Benzyl-2-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-
1
an oil. [α]2D0 ϭ Ϫ5.0 (c ϭ 1.0, CH3OH). H NMR (CD3OD): 0.91
(t, 3 H, CH3). 1.25Ϫ1.40 (m, 6 H, 3 CH2), 1.56 (m, 2 H,
decane-1,2-diol (14): This compound was obtained from β--galac-
tose pentaacetate (0.47 g, 1.2 mmol) and 5b (0.16 g, 0.6 mmol) as
described for compound 13. The reaction mixture was stirred at
room temperature for 2 h. Purification by flash chromatography
(petroleum ether/EtOAc, 7:3) gave 14 (0.28 g, 79%) as an oil.
OCH2CH2), 3.42Ϫ3.56 (m,
5 H, 2,3,5-H and OCH2CH2),
3.56Ϫ3.78 (m, 6 H, 6a,6b-H and CH2CHCH2), 3.82 (m, 1 H, 4-
H), 4.07 (m, 1 H, CH2CHCH2), 4.42 (d, J1,2 ϭ 7.5 Hz, 1 H, 1-H),
4.56 (m, 2 H, OCH2Ph), 7.05Ϫ7.08 (m, 5 H, Ph). 13C NMR
(CD3OD): 14.4, 23.7, 26.9, 30.7, 32.8, 62.5, 70.2, 71.4 (2 C), 72.7
(2 C), 74.4, 74.8, 76.8, 77.8, 104.6, 128.7Ϫ139.6 (C6H5). MS: m/
z ϭ 446 [M ϩ NH4]ϩ. C22H36O8 (428.5): calcd. C 61.66, H 8.47;
found C 61.46, H 8.40.
1
[α]2D0 ϭ ϩ7.0 (c ϭ 1.0, CHCl3). H NMR: δ ϭ 0.85 (t, 3 H, CH3),
1.16Ϫ1.41 (m, 12 H, 6 CH2), 1.46Ϫ1.64 (m, 2 H, CHCH2CH2),
1.95, 1.99, 2.01, and 2.12 (4 s, 12 H, OCOCH3), 3.44 (dd, J ϭ 9.5
Hz, J ϭ 5.5 Hz, 1 H, CHaHbOBzl), 3.63 (dd, J ϭ 4.5 Hz, 1 H,
CHaHbOBzl), 3.69 (m, 1 H, CH2CHCH2), 3.83 (t, J5,6b ϭ J5,6a
6.5 Hz, 1 H, 5-H), 4.08 (m, 2 H, 2 ϫ 6-H), 4.51 (s, 2 H, OCH2Ph),
4.56 (d, J1,2 ϭ 8.0 Hz, 1 H, 1-H), 4.98 (dd, J2,3 ϭ 10.5 Hz, J3,4
ϭ
(2R)-1-O-Benzyl-2-O-β-D-galactopyranosyldecane-1,2-diol (18): The
ϭ
procedure used to prepare 17 was utilized to convert a solution of
14 (0.27 g, 0.46 mmol) in 1 mL of methanol, into 18 in quantitative
yield. Waxy solid. [α]2D0 ϭ Ϫ4.0 (c ϭ 1.0, CH3OH). 1H NMR
(CD3OD): 0.90 (t, 3 H, CH3), 1.21Ϫ1.49 (m, 12 H, 6 CH2),
1.52Ϫ1.69 (m, 2 H, CHCH2CH2), 3.42Ϫ3.53 (m, 3 H, 2,3,5-H),
3.56 (dd, J ϭ 10.0 Hz, J ϭ 5.0 Hz, 1 H, CHaHbOBzl), 3.65 (dd,
J ϭ 4.5 Hz, 1 H, CHaHbOBzl), 3.72 (m, 2 H, 2 6-H), 3.83 (br. d,
3.5 Hz, 1 H, 3-H), 5.18 (dd, 1 H, 2-H), 5.35 (br. d, 1 H, 4-H),
7.18Ϫ7.40 (m, 5 H, Ph). 13C NMR: δ ϭ 14.7, 21.3 (4 C), 23.3, 25.8,
29.9, 30.2, 30.4, 32.5, 32.8, 62.0, 67.8, 70.0, 71.3, 71.7, 73.5, 74.0,
81.6, 102.4, 128.3Ϫ139.0 (C6H5), 169.9Ϫ171.0 (COCH3). MS:
m/z ϭ 612 [M ϩ NH4]ϩ. C31H46O11 (594.7): calcd. C 62.61, H 7.80;
found C 62.26, H 7.65.
3-O-Benzyl-1-O-hexyl-2-O-(2,3,4,6-tetra-O-acetyl-β-D-gluco-
J3,4 ϭ 3.0 Hz, 1 H, 4-H), 3.85 (m, 1 H, CH2CHCH2), 4.31 (d, J1,2 ϭ
pyranosyl)-sn-glycerol (15): This compound was obtained from β-
-glucose pentaacetate (0.59 g, 1.5 mmol) and 5a (0.20 g,
0.75 mmol) as described for 13. The reaction mixture was stirred
at room temperature for 1.5 h. After flash chromatography (petro-
leum ether/EtOAc, 7:3), 15 (0.37 g) was recovered in 83% yield as
7.5 Hz, 1 H, 1-H), 4.52 and 4.57 (2 d, J ϭ 12.0 Hz, 2 H, OCH2Ph),
7.04Ϫ7.08 (m, 5 H, Ph). 13C NMR (CD3OD): 14.4, 23.7, 26.1, 30.4,
30.6, 30.9, 32.6, 33.1, 62.4, 70.3, 72.7, 73.7, 74.3, 75.0, 76.6, 79.3,
104.5, 128.6Ϫ140.0 (C6H5). MS: m/z ϭ 444 [M ϩ NH4]ϩ.
C23H38O7 (426.5): calcd. C 64.76, H 8.98; found C 64.92, H 8.70.
1
an oil. [α]2D0 ϭ Ϫ9.2 (c ϭ 1.0, CH3OH). H NMR: δ ϭ 0.88 (t, 3
3-O-Benzyl-2-O-β-D-glucopyranosyl-1-O-hexyl-sn-glycerol (19): A
H, CH3), 1.22Ϫ1.34 (m, 6 H, 3 CH2), 1.53 (m, 2 H, OCH2CH2),
1.98, 2.00, 2.01, and 2.04 (4 s, 12 H, CH3CO), 3.38 (m, 2 H,
OCH2CH2), 3.41Ϫ3.66 (m, 5 H, 5-H and CH2CHCH2), 3.98 (m, 1
H, CH2CHCH2), 4.09 (dd, J6a,6b ϭ 12.0 Hz, J5,6b ϭ 2.0 Hz, 1 H,
6b-H), 4.20 (dd, J5,6a ϭ 5.0 Hz, 1 H, 6a-H), 4.52 (s, 2 H, OCH2Ph),
4.78 (d, J1,2 ϭ 8.0 Hz, 1 H, 1-H), 4.96 (dd, J2,3 ϭ 9.0 Hz, 1 H, 2-
H), 5.05 (dd, J3,4 ϭ J4,5 ϭ 9.5 Hz, 1 H, 4-H), 5.18 (dd, 1 H, 3-H),
7.20Ϫ7.40 (m, 5 H, Ph). 13C NMR: δ ϭ 14.7, 21.2Ϫ21.4 (COCH3),
23.3, 26.5, 30.3, 32.3, 62.8, 69.3, 70.9, 72.2, 72.3, 72.4, 72.5, 73.6,
74.0, 78.9, 101.3, 128.2Ϫ139.0 (C6H5), 170.0Ϫ171.3 (COCH3). MS:
m/z ϭ 614 [M ϩ NH4]ϩ. C30H44O12 (596.7): calcd. C 60.39, H 7.43;
found C 60.67, H 7.30.
solution of 15 (0.36 g, 0.60 mmol) in methanol (2 mL) was treated
for 1.5 h at room temperature with the same procedure as used for
17 to give 19 quantitatively as an oil. [α]2D0 ϭ Ϫ14.6 (c ϭ 1.0,
1
CH3OH). H NMR (CD3OD): 0.91 (t, 3 H, CH3), 1.23Ϫ1.40 (m,
6 H, 3 CH2), 1.55 (m, 2 H, OCH2CH2), 3.20 (dd, J1,2 ϭ 8.0 Hz,
J2,3 ϭ 8.5 Hz, 1 H, 2-H), 3.23Ϫ3.39 (m, 3 H, 3,4,5-H), 3.47 (m, 2
H, OCH2CH2), 3.57Ϫ3.70 (m, 5 H, 6b-H and CH2CHCH2), 3.85
(dd, J5,6a ϭ 2.0 Hz, J6a,6b ϭ 12.0 Hz, 1 H, 6a-H), 4.07 (m, 1 H,
CH2CHCH2), 4.48 (d, 1 H, 1-H), 4.56 (s, 2 H, OCH2Ph), 7.04Ϫ7.08
(m, 5 H, Ph). 13C NMR (CD3OD): 14.4, 23.7, 26.9, 30.7, 32.8, 62.8,
71.4 (2 C), 71.6, 72.7, 74.4, 75.2, 77.9 (2 C), 78.0, 103.8,
128.7Ϫ139.5 (C6H5). MS: m/z ϭ 446 [M ϩ NH4]ϩ. C22H36O8
(428.5): calcd. C 61.66, H 8.47; found C 61.94, H 8.39.
(2R)-1-O-Benzyl-2-O-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-
decane-1,2-diol (16): The reaction was carried out as described for
the synthesis of compound 13, starting from β--glucose pentaacet-
ate (0.33 g, 0.84 mmol) and 5b (0.11 g, 0.42 mmol). Compound 16
(2R)-1-O-Benzyl-2-O-β-
D-glucopyranosyldecane-1,2-diol (20): This
compound was obtained quantitatively as an oil from 16 (0.15 g,
(0.15 g, 60%) was obtained after flash chromatography (petroleum 0.25 mmol), as described for 17. [α]2D0 ϭ Ϫ13.0 (c ϭ 1, CH3OH).
ether/EtOAc, 8:2, then 7:3) as an amorphous white solid. [α]2D0
ϭ
1H NMR (CD3OD): 0.89 (t, 3 H, CH3), 1.21Ϫ1.47 (m, 12 H, 6
Ϫ1.0 (c ϭ 1.0, CHCl3). 1H NMR: δ ϭ 0.86 (t, 3 H, CH3), CH2), 1.52Ϫ1.68 (m, 2 H, CHCH2CH2), 3.18 (dd, J1,2 ϭ 8.0 Hz,
1.16Ϫ1.60 (m, 14 H, 7 CH2), 1.97, 1.99, 2.00, and 2.03 (4 s, 12 H, J2,3 ϭ 9.0 Hz, 1 H, 2-H), 3.22Ϫ3.39 (m, 3 H, 3,4,5-H), 3.57 (dd,
CH3CO), 3.43 (dd, J ϭ 10.0 Hz, J ϭ 5.5 Hz, 1 H, CHaHbOBzl), J ϭ 10.5, J ϭ 5.0 Hz, 1 H, CHaHbOBzl), 3.62Ϫ3.69 (m, 2 H, 6b-
3.57Ϫ3.65 (m, 2 H, 5-H and CHaHbOBzl), 3.69 (m, 1 H, H and CHaHbOBzl), 3.81Ϫ3.89 (m, 2 H, 6a-H and CH2CHCH2),
CH2CHCH2), 4.05 (dd, J6a,6b ϭ 12.0 Hz, J5,6b ϭ 2.0 Hz, 1 H, 6b-
4.35 (d, 1 H, 1-H), 4.54 and 4.58 (2 d, 2 H, OCH2Ph), 7.03Ϫ7.09
H), 4.17 (dd, J5,6a ϭ 4.5 Hz, 1 H, 6a-H), 4.50 (s, 2 H, OCH2Ph), (m, 5 H, Ph). 13C NMR (CD3OD): 14.4, 23.7, 26.1, 30.4, 30.6,
4.59 (d, J1,2 ϭ 8.0 Hz, 1 H, 1-H), 4.96 (dd, J2,3 ϭ 9.5 Hz, 1 H, 2-
30.9, 32.6, 33.1, 62.9, 71.7, 73.7, 74.4, 75.2, 77.9, 78.0, 79.5, 103.8,
1434
Eur. J. Org. Chem. 2002, 1429Ϫ1435