D. Crich et al. / Tetrahedron 58 (2002) 35±44
43
(46 mg, 0.38mmol), and pyridine (0.03 mL, 0.38mmol) in
dry CH2Cl2 (5.0 mL) was added lauroyl chloride (0.088 mL,
0.38mmol) at room temperature under Ar. After stirring for
5 h the reaction mixture was quenched with water (1.0 mL),
diluted with CH2Cl2 (5.0 mL), washed with saturated
NaHCO3 solution (10 mL), water (10 mL), and brine
(10 mL). The organic layer was dried, ®ltered, concentrated
in vacuo and puri®ed by ¯ash column chromatography on
silica gel (eluent: EtOAc/hexanes2:8) to give 27 (0.160 g,
J6.3 Hz, 6H); 13C NMR d 173.2, 170.8, 169.5, 135.7,
135.6, 133.5, 133.4, 129.9, 128.3, 127.9, 125.6, 106.9,
100.1, 97.2, 72.3, 71.0, 68.7, 66.0, 65.0, 62.4, 60.4, 34.2,
34.1, 32.0, 29.8, 29.7, 29.6, 29.5, 29.4, 29.2, 29.1, 26.8,
25.8, 25.1, 24.8, 22.8, 20.8, 14.2, 11.8; ESI HRMS Calcd
for C54H84O11Si [M1Na1]: 959.5681. Found: 959.5682.
3.4.9. 4-O-(4,6-Di-O-acetyl-2,3-di-O-dodecyl-b-d-manno-
pyranosyl)-1-O-tert-butyldiphenylsilyl-d-erythritol (30)
and 1-O-(4,6-di-O-acetyl-2,3-di-O-dodecyl-b-d-manno-
pyranosyl)-4-O-tert-butyldiphenylsilyl-d-erythritol (31).
To a stirred solution of OsO4 (0.015 mL, 0.0064 mmol),
and NMO (0.012 g, 0.089 mmol) in acetone±water (2:1
v/v) was added the alkene 29 (0.056 g, 0.060 mmol) in
acetone (3.0 mL) at room temperature. The resulting
reaction mixture was stirred for 24 h before Na2S2O3
(0.037 g, 0.24 mmol) was added. The mixture was then
stirred for a further 1.5 h before the acetone was removed
under vacuum and EtOAc (15 mL) and H2O (15 mL) were
added to the residue. The water phase was saturated with
NaCl and then extracted with EtOAc. The combined organic
phases were washed with water (10 mL), brine (10 mL),
dried and concentrated to dryness. Flash column chromato-
graphy on silica gel (eluent: EtOAc/hexanes3:7) gave 30
and 31 (0.041 g, 70%) as an inseparable 1:1 mixture in the
98%): [a]23 234.38 (c 1.6; 1H NMR d 7.7 (m, 4H), 7.5±
D
7.25 (m, 11H), 5.83±5.76 (m, 1H), 5.62 (s, 1H), 5.54 (d,
J3.0 Hz, 1H), 5.11 (m, 2H), 4.56 (s, 1H), 4.23±4.08(m,
5H), 3.94 (t, J10.0 Hz, 1H), 3.82 (t, J10.2 Hz, 1H),
3.37±3.29 (m, 1H), 2.42 (t, J7.2 Hz, 2H), 2.24 (t,
J7.2 Hz, 2H), 1.69±1.53 (m, 4H), 1.23 (b s, 32H), 1.04
(s, 9H), 0.87 (t, J7 Hz, 6H); 13C NMR d 173.0, 172.8,
137.2, 135.7, 133.5, 133.3, 130.0, 129.9, 129.2, 128.3,
127.9, 126.2, 125.6, 101.8, 97.8, 75.9, 70.1, 69.3, 68.5,
67.2, 65.2, 60.5, 53.2, 34.2, 34.1, 32.0, 29.8, 29.7, 29.6,
29.5, 29.4, 29.2, 29.1, 26.9, 25.2, 24.8, 22.8, 19.2, 14.27;
ESI HRMS Calcd for C57H84O9Si [M1Na1]: 963.5782.
Found: 953.5782.
3.4.7. 4-tert-Butyldiphenylsiloxy-2Z-buten-1-yl 2,3-di-O-
dodecyl-b-d-mannopyranoside (28). Compound 27
(0.100 g, 0.11 mmol) was dried under vacuum for 1 h then
treated with a 1% solution of iodine in methanol (3 mL) and
heated to 708C for 3 h. After cooling to room temperature
the reaction was quenched with sodium thiosulfate solution
(1.0 mL), and concentrated under vacuum. The residue was
extracted with chloroform (2£5 mL) and the extracts dried
and concentrated to dryness. Flash column chromatography
1
form of an oil: H NMR d 7.6±7.7 (m, 4H), 7.3±7.5 (m,
6H), 5.48(m, 1H), 5.22 (m, 1H), 5.05 (m, 1H), 4.66 (s, 1H),
4.24±4.11 (m, 2H), 4.01 (m, 1H), 3.87±3.64 (m, 6H), 2.6
(m, 1H), 2.40 (t, J7.5 Hz, 2H), 2.21 (t, J7.8Hz, 2H),
2.04 (2s, 3H), 2.02 (s, 6H), 1.64±1.50 (m, 4H), 1.24 (bs,
32H), 1.55 (s, 9H), 0.87 (t, J9.9 Hz, 6H); 13C NMR d
172.8, 135.6, 133.0, 130.0, 127.9, 99.6, 73.7, 73.0, 72.5,
71.8, 71.7, 71.2, 70.7, 70.6, 68.8, 68.7, 66.1, 66.0, 65.0,
62.6, 34.2, 34.1, 32.0, 29.8, 29.6, 29.5, 29.4, 29.2, 27.0,
25.1, 24.8, 22.8, 20.8, 19.4, 14.2; ESI HRMS Calcd for
C54H86O13Si [M1Na1]: 993.5735. Found: 993.5738.
on silica gel (eluent: EtOAc/hexanes1:1) then gave 28
1
(0.047 g, 51%) as a yellow oil: [a]23 211.78 (c 5.0); H
D
NMR d 7.7±7.6 (m, 4H), 7.5±7.3 (m, 6H), 5.80±5.74 (m,
1H), 5.54±5.45 (m, 1H), 5.40 (d, J3.0 Hz, 1H), 4.83 (dd,
J3.3, 9.9 Hz, 1H), 4.52 (d, J1.2 Hz, 1H), 4.22±3.77 (m,
7H), 3.25±3.19 (m, 1H), 2.36 (t, J7.5 Hz, 3H), 2.27 (t,
J7.2 Hz, 3H), 1.63±1.47 (m, 4H), 1.24 (b s, 32H), 1.03
(s, 9 H), 0.87 (t, J6.6 Hz, 6H); 13C NMR d 173.6, 173.0,
135.7, 135.6, 133.5, 133.2, 129.9, 128.4, 127.9, 125.7, 97.4,
75.7, 73.9, 68.9, 66.2, 65.1, 62.4, 60.4, 34.2, 32.0, 29.7,
29.6, 29.5, 29.4, 29.2, 26.8, 25.2, 24.7, 22.8, 19.2, 14.2;
ESI HRMS Calcd for C50H80O9Si [M1Na1]: 875.5469.
Found: 875.5474.
3.4.10. 4-O-(4,6-Di-O-acetyl-2,3-di-O-dodecyl-b-d-manno-
pyranosyl)-d-erythritol (32) and 1-O-(4,6-di-O-acetyl-
2,3-di-O-dodecyl-b-d-mannopyranosyl)-d-erythritol (22).
To a solution of the diols 30 and 31 (0.015 g, 0.015 mmol)
in THF (3.0 mL) at 08C, under Ar, was added TBAF 1 M in
THF (0.008mL, 0.031 mmol). The reaction mixture was
stirred at room temperature for 4 h, then quenched with
water (1.0 mL), and the organic layer washed with saturated
NaHCO3 solution (2£10 mL), H2O (1£10 mL), and brine
(1£50 mL), dried and concentrated to dryness. Flash
column chromatography on silica gel (EtOAc/
hexanes6:4) gave an inseparable 1:1 mixture of 32 and
22 (0.011 g, 97%) as a microanalytically pure yellow oil.
Anal. Calcd for C36H68O13: C, 62.27; H, 9.35. Found: C,
62.39; H, 9.29. The spectral data of 22 were as presented
3.4.8. 4-tert-Butyldiphenylsiloxy-2Z-buten-1-yl 4,6-di-O-
acetyl-2,3-di-O-dodecyl-b-d-mannopyranoside (29). To a
solution of diol 28 (0.080 g, 0.094 mmol) in pyridine
(0.151 mL) was added acetic anhydride (0.175 mL,
1.88 mmol) at room temperature. The reaction mixture
was then stirred for 4 h, before it was diluted with ether
(10 mL), washed twice each with 1 M HCl (10 mL), 1 M
NaOH (10 mL) and water (10 mL), once with brine
(10 mL), dried, and concentrated under vacuum. Puri®ca-
tion of the residue by chromatography on silica gel (eluent:
1
above. The data of 32 were extracted from the mixture: H
NMR (500 MHz) d 5.54 (dd, J3.2, 0.7 Hz, 1H), 5.28(t,
J10.1 Hz, 1H), 5.10 (dd, J3.3, 9.8Hz, 1H), 4.74 (d,
J0.7 Hz, 1H), 4.27 (dd, J5.7, 12.4 Hz, 1H), 4.22 (dd,
J2.4, 12.4 Hz, 1H), 4.02 (dd, J3.1, 10.6 Hz, 1H), 3.87
(dd, J5.7, 10.6 Hz 1H), 3.80 (dd, J3.9, 11.4 Hz, 1H),
3.77±3.66 (m, 4H), 2.45 (dt, J2.9, 7.5 Hz, 2H), 2.30 (b
s, 2H), 2.25 (t, J7.5 Hz, 2H), 2.12 (s, 3H), 2.06 (s, 3H),
1.67 (m, 2H), 1.58(m, 2H), 1.20±1.40 (b s, 32H), 0.90 (m,
6H); 13C NMR d 173.8, 173.1, 171.1, 169.8, 99.7, 72.9,
72.8, 72.0, 71.6, 71.0, 68.8, 66.2, 64.0, 63.0, 34.5, 34.4,
EtOAc/hexanes1:9) afforded 29 (0.082 g, 93%):
1
[a]23 214.88 (c 1.0); H NMR d 7.6±7.7 (m, 4H), 7.5±
D
7.3 (m, 6H), 5.80±5.74 (m, 1H), 5.60±5.45 (m, 1H), 5.40 (d,
J3.3 Hz, 1H), 5.21 (t, J10.0 Hz, 1H), 4.99 (dd, J2.7,
12.3 Hz, 2H), 4.30±3.90 (m, 6H), 3.45 (m, 1H), 2.40 (t,
J7.8Hz, 2H), 2.20 (t, J7.5 Hz, 2H), 2.00 (s, 6H),
1.64±1.50 (m, 4H), 1.24 (b s, 32H), 1.03 (s, 9H), 0.87 (t,