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38.24, 26.76, 18.96, 17.05, 14.69. HRMS (pos. ion ESI) m/z calcd for
7.38–7.69 (m, 10H, Ph  2), 5.81–5.83 (m, 1H, CH2@CH), 5.02–5.08
(m, 2H, CH2@CH), 4.60 (s, 2H, MOM-CH2), 3.83–3.91, 3.69–3.73 (each
m, each 2H, CH2OTBDPS or CH2OMOM), 3.35 (s, 3H, MOM-CH3),
2.31–2.32 (m, 2H, CH2@CHCH2), 1.75–1.87 (m, 4H, CH2CH2O Â 2),
1.05 (s, 9H, t-Bu); 13C NMR (100 MHz, CDCl3) d 135.42, 134.06,
132.80, 129.71, 127.65, 117.79, 96.32, 73.27, 63.93, 60.94, 55.14,
44.22, 39.81, 38.21, 26.67, 18.86. HRMS (pos. ion ESI) m/z calcd for
(M+Na)+ C26H38NaO4Si: 465.24316. Found: 465.24243.
(M+Na)+ C26H40NaO4Si: 467.25881. Found: 467.25863.
6.10. 1-O-(tert-Butyldiphenylsilyl)-3-(2-methoxymethyloxyeth-
yl)heptan-1,3,-diol (11d)
Compound 11d (248 mg, quant.) was obtained as a colorless oil
from 10 (200 mg, 500 l
mol): 1H NMR (400 MHz, CDCl3) d 7.38–7.69
(m, 10H, Ph  2), 4.60 (s, 2H, MOM-CH2), 3.84–3.89, 3.63–3.70 (each
m, each 2H, CH2OTBDPS, CH2OMOM), 3.78 (s, 1H, OH), 3.36 (s, 3H,
MOM-CH3), 1.73–1.88 (m, 4H, CH2CH2O Â 2, CH3CH2CH2), 1.45–1.51
(m, 2H, CH3CH2CH2CH2), 1.21–1.29 (m, 4H, CH3CH2CH2CH2,
CH3CH2CH2CH2), 1.05 (s, 9H, t-Bu), 0.89 (t, 3H, CH3CH2CH2CH2,
J = 6.4 Hz); 13C NMR (100 MHz, CDCl3) d 135.54, 132.96, 132.94,
129.79, 127.74, 96.47, 73.68, 64.26, 61.18, 55.29, 39.87, 39.25,
38.23, 26.76, 25.99, 23.26, 18.96, 14.05. HRMS (pos. ion ESI) m/z calcd
for (M+Na)+ C27H42NaO4Si: 481.27446. Found: 481.27322.
6.15. 1-O-(tert-Butyldiphenylsilyl)-3-ethynyl-5-O-methoxym-
ethylpentan-1,3,5-triol (11j)
Compound 11j (1.55 g, 79%) was obtained as a light yellow oil
from 10 (1.83 g, 4.58 mmol): 1H NMR (500 MHz, CDCl3) d 7.36–
7.73 (m, 10H, Ph  2), 4.80 (s, 1H, OH), 4.63 (s, 2H, MOM-CH2),
4.20–4.25, 3.81–3.97 (each m, 1H and 3H, CH2OTBDPS or CH2O-
MOM), 3.37 (s, 3H, MOM-CH3), 2.50 (s, 1H, ethynyl-H), 2.06–2.12,
1.97–2.02, 1.83–1.87 (each m, 2H, 1H, and 1H, CH2CH2O Â 2),
1.05 (s, 9H, t-Bu); 13C NMR (125 MHz, CDCl3) d 135.49, 135.42,
132.62, 129.73, 129.71, 127.66, 127.61, 96.36, 85.44, 73.04, 70.34,
64.43, 61.79, 55.19, 42.64, 41.43, 26.63, 18.87. HRMS (pos. ion
ESI) m/z calcd for (M+Na)+ C25H34NaO4Si: 449.21186. Found:
449.21144.
6.11. 1-O-(tert-Butyldiphenylsilyl)-3-(2-methoxymethyloxyeth-
yl)-5-methylhexan-1,3,-diol (11e)
Compound 11e (2.73 g, 85%) was obtained as a colorless oil
from 10 (2.80 g, 7.00 mmol): 1H NMR (400 MHz, CDCl3) d 7.38–
7.69 (m, 10H, Ph  2), 4.60 (s, 2H, MOM-CH2), 3.84–3.87, 3.63–
3.71 (each m, each 2H, CH2OTBDPS, CH2OMOM), 3.35 (s, 3H,
MOM-CH3), 1.71–1.89 (m, 5H, CH2CH2O Â 2, (CH3)2CHCH2), 1.39–
1.42 (m, 2H, (CH3)2CHCH2), 1.05 (s, 9H, t-Bu), 0.92–0.96 (m, 6H,
6.16. 1-O-(tert-Butyldiphenylsilyl)-3-(2-methoxymethyloxyeth-
yl)-4-hexyn-1,3,-diol (11k)
(CH3)2CHCH2); 13C NMR (100 MHz, CDCl3)
d
135.44, 132.83,
Compound 11k (1.36 g, 77%) was obtained as a colorless oil
from 10 (1.60 g, 4.00 mmol): 1H NMR (500 MHz, CDCl3) d 7.38–
7.74 (m, 10H, Ph  2), 4.63 (s, 2H, MOM-CH2), 4.18–4.23, 3.79–
3.95 (each m, 1H and 3H, CH2OTBDPS or CH2OMOM), 3.37 (s, 3H,
MOM-CH3), 2.03–2.08, 1.92–1.96, 1.78–1.83 (each m, 2H, 1H, and
1H, CH2CH2O Â 2), 1.85 (s, 3H, Me), 1.05 (s, 9H, t-Bu); 13C NMR
132.82, 129.69, 127.64, 96.36, 74.10, 64.30, 61.16, 55.18, 47.90,
40.32, 38.81, 26.66, 24.68, 23.79, 18.86. HRMS (pos. ion ESI) m/z
calcd for (M+Na)+ C27H42NaO4Si: 481.27446. Found: 481.27385.
6.12. 1-O-(tert-Butyldiphenylsilyl)-5-O-methoxymethyl-3-
cyclopropyl-pentan-1,3,5-triol (11f)
(100 MHz, CDCl3) d 135.52, 135.47, 132.80, 132.71, 129.72,
129.68, 127.67, 127.64, 96.37, 81.00, 80.82, 70.52, 64.72, 62.03,
55.12, 43.03, 41.83, 26.65, 18.89, 3.47. HRMS (pos. ion ESI) m/z
calcd for (M+Na)+ C26H36NaO4Si: 463.22751. Found: 463.22726.
Compound 11f (0.43 g, 89%) was obtained as a colorless oil from
10 (0.96 g, 3.90 mmol): 1H NMR (500 MHz, CDCl3) d 7.67–7.70 (m,
4H, Ph), 7.38–7.44 (m, 6H, Ph), 4.61 (s, 2H, MOM-CH2), 3.83–3.89,
3.75–3.81 (each m, each 2H, CH2OTBDPS, CH2OMOM), 3.76 (s, 1H,
OH), 3.36 (s, 3H, MOM-CH3), 1.93–1.87 (m, 2H, CH2CH2O), 1.78–
1.75 (m, 2H, CH2CH2O), 1.04 (s, 9H, t-Bu), 0.69 (m, 1H, CH of cyclo-
propyl), 0.52–0.43 (m, 2H, CH2 of cyclopropyl), 0.34–0.32 (d, 2H,
CH2 of cyclopropyl, J = 8.5 Hz): 13C NMR (125 MHz, CDCl3) d
135.74, 133.14, 129.99, 127. 93, 96.71, 71.69, 64.82, 61.86, 60.56,
55.49, 42.25, 41.30, 26.98, 19.13. HRMS (pos. ion ESI) m/z calcd
for (M+Na)+ C26H38NaO4Si: 465.24316. Found: 465.24308.
6.17. Deprotection of the MOM group
A mixture of the Grignard products and ZrCl4 (0.5 equiv) in i-
PrOH (as a 1 mM solution) was stirred at 90 °C for 30 min. The mix-
ture was partitioned between AcOEt and H2O, and the organic layer
was washed with brine, dried with Na2SO4, and evaporated. The
residue was purified by silica gel column chromatography (25%
AcOEt in hexane) to give the corresponding alcohols.
6.13. 1-O-(tert-Butyldiphenylsilyl)-5-O-methoxymethyl-3-(1-
6.18. 1-O-(tert-Butyldiphenylsilyl)-3-vinylpentan-1,3,5-triol (12a)
methylvinyl)pentan-1,3,5-triol (11g)
Compound 12a (1.42 g, 78%) was obtained as a colorless oil
from 11a (2.02 g, 4.72 mmol): 1H NMR (300 MHz, CDCl3) d 7.39–
7.68 (m, 10H, Ph  2), 5.76 (dd, 1H, CH2@CH, Jtrans = 22.8 Hz,
Jcis = 13.6 Hz), 5.56 (dd, 1H, CH2@CH (trans), Jvicinal = 22.8 Hz,
Jgeminal = 1.6 Hz), 5.33 (dd, 1H, CH2@CH (cis), Jvicinal = 13.6 Hz,
Jgeminal = 1.6 Hz), 4.72 (s, 1H, OH), 3.73–3.96 (m, 4H, CH2OH,
CH2OTBDPS), 3.32 (br s, 1H, OH), 1.52–2.14 (m, 4H, CH2CH2O Â 2),
1.04 (s, 9H, t-Bu); 13C NMR (100 MHz, CDCl3) d 142.01, 135.45,
135.42, 132.26, 132.22, 129.91, 129.87, 127.79, 127.71, 114.72,
78.04, 61.90, 59.50, 41.96, 40.71, 26.60, 18.82. HRMS (pos. ion
ESI) m/z calcd for (M+Na)+ C23H32NaO3Si: 407.20129. Found:
407.20051.
Compound 11g (2.52 g, 85%) was obtained as a colorless oil
from 10 (2.67 g, 6.66 mmol): 1H NMR (400 MHz, CDCl3) d 7.37–
7.67 (m, 10H, Ph  2), 5.24, 4.99 (each s, each 1H, CH2@C), 4.60
(s, 2H, MOM-CH2), 4.28 (br s, 1H, OH), 3.53–3.87 (m, 4H,
CH2OTBDPS, CH2OMOM), 3.35 (s, 3H, MOM-CH3), 1.71–2.03 (m,
4H, CH2CH2O Â 2), 1.61 (s, 3H, Me), 1.03 (s, 9H, t-Bu); 13C NMR
(100 MHz, CDCl3)
d 147.11, 135.43, 135.41, 132.72, 132.70,
129.68, 129.65, 127.63, 127.58, 112.20, 96.46, 77.34, 64.06, 61.32,
55.13, 39.89, 38.72, 26.60, 19.53, 18.84. HRMS (pos. ion ESI) m/z
calcd for (M+Na)+ C26H38NaO4Si: 465.24316. Found: 465.24369.
6.14. 1-O-(tert-Butyldiphenylsilyl)-3-(2-methoxymethyloxyeth-
yl)-5-hexen-1,3,-diol (11i)
6.19. 1-O-(tert-Butyldiphenylsilyl)-3-ethylpentan-1,3,5-triol (12b)
Compound 11i (1.78 g, quant.) was obtained as a light yellow oil
Compound 12b (1.09 g, 68%) was obtained as a light yellow oil
from 10 (1.60 g, 4.00 mmol): 1H NMR (400 MHz, CDCl3)
d
from 11b (1.79 g, 4.17 mmol): 1H NMR (400 MHz, CDCl3)
d