110.2, 83.6, 79.8, 72.4, 72.0, 70.9, 70.9, 27.2 and 20.9; m/z 684
(Mϩ, 0.6%), 669 (4.7), 535 (5.9), 507 (5.1), 456 (5.5), 291 (5.2),
105 (100), 91 (95) and 77 (22).
and 12-H), 0.98–0.94 (4H, m, TMSCH2CH2) and 0.02 (18H,
s, Me); δC 137.5, 128.3, 127.8, 127.7, 93.9, 83.3, 79.7, 72.9,
71.3, 69.1, 66.8, 24.2, 18.1 and Ϫ1.4; m/z 696 (Mϩ, 1.2%), 548
(6.0), 429 (12), 91 (100) and 73 (100).
(1R,2S,3S,4R,8S,9S)-1,4-Bis(benzoyloxy)-8,9-bis(benzyloxy)-
cyclododeca-6,10-diyne-2,3-diol (؉)-19
(1R,2R,3S,4R,8S,9S)-4-Triethylsiloxy-2,3-bis[(trimethylsilyl-
ethoxymethyl)oxy]-8,9-bis(benzyloxy)cyclododeca-6,10-diyn-1-
ol (؉)-22
A solution of 18 (83.0 mg, 0.12 mmol) in MeOH (2.0 cm3) and
THF (2.00 cm3) in the presence of conc. HCl (1.0 cm3) was
stirred for 24 h at rt and the solvent was evaporated off. The
residue was taken up in AcOEt, which was washed with 10%
aq. NaOH, water and brine, dried and concentrated to dry-
ness. The residue was chromatographed with hexane–AcOEt
(2:1) to give (ϩ)-19 (55.0 mg, 70%) as a colorless solid,
mp 46–47 ЊC (from hexane–AcOEt) (Found: C, 74.2; H, 5.6.
C40H36O8 requires C, 74.5; H, 5.6%); [α]D25 ϩ12.3 (c 0.50,
TESCl (6.20 mg, 0.04 mmol) was added to a solution of 21
(21.0 mg, 0.03 mmol) and imidazole (10.0 mg, 0.15 mmol) in
CH2Cl2 (0.5 cm3) and the mixture was stirred at rt for 7 h,
quenched by addition of water and diluted with CH2Cl2. The
CH2Cl2 solution was washed with water and brine, dried and
concentrated to dryness. Chromatography of the residue with
hexane–AcOEt afforded (ϩ)-22 (9.30 mg, 38%) and recovery of
the starting material 21 (11.0 mg, 52%). Compound (ϩ)-22
was obtained as a colorless oil (Found: Mϩ ϩ 23, 833.4279.
C44H70O8Si3Na requires M ϩ 23, 833.4276); [α]D26 ϩ82.7 (c 0.20,
CHCl3); νmax/cmϪ1 3525 (OH), 2220 (C᎐C) and 1719 (CO);
᎐
᎐
δH 8.07–8.05 (4H, m, aromatic H), 7.54 (2H, m, aromatic H),
7.39–7.27 (14H, m, aromatic H), 5.25 (2H, m, 1H and 4-H),
4.80 (2H, m, 2-H and 3-H), 4.77, 4.56 (4H, AB-q, J 11.7,
benzylic H), 4.36 (2H, s, 8-H and 9-H), 3.16 (2H, d, J 6.8,
OH), 3.02 (2H, dd, J 17.6 and 5.9, 5-H and 12-H) and 2.82
(2H, m, 5-H and 12-H); δC 166.0, 137.3, 133.4, 129.7, 129.6,
128.6, 128.4, 127.9, 127.8, 83.4, 80.1, 73.7, 72.2, 71.0, 69.2 and
21.8; m/z 644 (Mϩ, 0.8%), 614 (0.8), 535 (7.4), 307 (14), 105
(100), 91 (100) and 77 (52).
CHCl3); νmax/cmϪ1 3520 (OH) and 2220 (C᎐C); δ 7.36–7.25
᎐
᎐
H
(10H, m, aromatic H), 4.89–4.56 (8H, m, benzylic H and
OCH2O), 4.45 (1H, m, 2-H), 4.34 (2H, s, 8-H and 9-H), 4.16
(1H, m, 1-H), 4.01 (1H, m, 4-H), 3.96 (1H, dd, J 7.3 and 4.4,
3-H), 3.80–3.54 (4H, m, TMSCH2CH2), 3.46 (1H, m, OH),
2.76–2.54 (4H, m, 5-H and 12-H), 0.98 (9H, t, J 7.8, Me), 0.98–
0.93 (4H, m, TMSCH2CH2), 0.64 (6H, q, J 7.8, MeCH2), 0.02
(9H, s, Me) and 0.01 (9H, s, Me); δC 137.7, 137.6, 128.3, 128.0,
127.9, 127.6, 96.8, 96.7, 85.3, 85.1, 79.7, 79.6, 76.8, 76.3, 72.7,
72.5, 72.2, 70.9, 70.9, 70.6, 66.3, 66.1, 24.9, 23.4, 18.2, 18.1, 6.8,
4.9, Ϫ1.4 and Ϫ1.5; FABMS m/z 833 (Mϩ ϩ 23, 0.3%), 226
(4.8), 91 (48) and 73 (100).
(1R,2S,3S,4R,8S,9S)-1,4-Bis(benzoyloxy)-2,3-bis[(trimethyl-
silylethoxymethyl)oxy]-8,9-bis(benzyloxy)cyclododeca-6,10-
diyne (؉)-20
SEMCl (179 mg, 1.06 mmol) was added to a solution of 19
(68.0 mg, 0.11 mmol) and DIPEA (196 mg, 2.12 mmol) in
CH2Cl2 (1.0 cm3) at rt. After being refluxed for 5 h, the
reaction mixture was quenched by addition of water and
extracted with CH2Cl2. The extract was washed with water
and brine, dried and concentrated to dryness. Chromato-
graphy of the residue with hexane–AcOEt (13:1) afforded
(ϩ)-20 (75.0 mg, 79%) as a colorless oil (Found: C, 68.8; H,
7.3. C52H64O10Si2 requires C, 69.0; H, 7.1%); [α]2D7 ϩ60.8 (c 0.50,
(2S,3S,4R,8S,9S)-4-Triethylsiloxy-2,3-bis[(trimethylsilyl-
ethoxymethyl)oxy]-8,9-bis(benzyloxy)cyclododeca-10,11-dien-
6-yn-1-one (؉)-23
A solution of DMSO (76.0 mg, 1.02 mmol) in CH2Cl2 (0.5 cm3)
was gradually added to a solution of (CF3CO)2O (104 mg, 0.51
mmol) in CH2Cl2 (0.5 cm3) at Ϫ78 ЊC. After stirring of the
CH2Cl2 solution for 15 min, a solution of the alcohol 22 (81.0
mg, 0.10 mmol) in CH2Cl2 (0.5 cm3) was added and the reaction
mixture was stirred at the same temperature for 1 h. Et3N (152
mg, 1.53 mmol) was added to the reaction mixture, which was
then gradually warmed to rt and quenched by addition of water
and extracted with CH2Cl2. The extract was washed with water
and brine, dried and concentrated to dryness. Chromatography
of the residue with hexane–AcOEt (20:1) afforded (ϩ)-23 (65.0
mg, 81%) as a colorless oil (Found: Mϩ ϩ 23, 831.4113.
C44H68O8Si3Na requires M ϩ 23, 831.4120); [α]D23 ϩ73.4 (c 0.20,
CHCl3); νmax/cmϪ1 2230 (C᎐C) and 1719 (CO); δ 8.06–7.26
᎐
᎐
H
(20H, m, aromatic H), 5.45 (2H, m, 1-H and 4-H), 4.87,
4.85 (4H, AB-q, J 6.8, OCH2O), 4.80, 4.59 (4H, AB-q, J 11.7,
benzylic H), 4.67 (2H, m, 2-H and 3-H), 4.41 (2H, s, 8-H and
9-H), 3.71–3.55 (4H, m, TMSCH2CH2), 2.99 (2H, dd, J 17.1
and 6.8, 5-H and 12-H), 2.86 (2H, d, J 17.1, 5-H and 12-H),
0.89–0.85 (4H, m, TMSCH2CH2) and Ϫ0.05 (18H, s, Me);
δC 165.5, 137.5, 133.1, 129.9, 129.8, 128.4, 128.3, 127.9, 127.7,
96.4, 83.9, 79.9, 76.0, 72.8, 72.5, 70.9, 66.2, 21.2, 17.9 and
Ϫ1.5; FABMS m/z 927 (Mϩ ϩ 23, 0.6%), 105 (50), 91 (52), 73
(100) and 55 (17).
CHCl3); νmax/cmϪ1 2230 (C᎐C), 1952 (᎐C᎐) and 1675 (CO);
᎐
᎐
᎐ ᎐
δH 7.37–7.27 (10H, m, aromatic H), 5.97 (1H, dd, J 6.3 and 3.3,
12-H), 5.91 (1H, dd, J 6.3 and 4.6, 10-H), 5.11 (1H, d, J 7.9,
2-H), 4.87–4.48 (9H, m, 3-H, benzylic H and OCH2O), 4.38
(1H, d, J 5.9, 8-H), 4.32 (1H, m, 4-H), 4.23 (1H, m, 9-H), 3.73–
3.46 (4H, m, TMSCH2CH2), 2.90 (1H, m, 5-H), 2.38 (1H, m,
5-H), 0.96 (9H, t, J 7.6, Me), 0.96–0.79 (4H, m, TMSCH2CH2),
0.60 (6H, q, J 7.6, CH2Me), 0.00 (9H, s, Me) and Ϫ0.02 (9H, s,
Me); δC 213.6, 197.6, 137.6, 175.5, 128.4, 128.3, 127.9, 127.8,
127.8, 127.7, 99.0, 96.5, 95.8, 95.3, 85.6, 81.3, 78.7, 76.3, 75.8,
72.0, 71.4, 70.7, 70.6, 65.6, 65.4, 22.8, 18.0, 17.9, 6.8, 4.7, Ϫ1.4
and Ϫ1.5; FABMS m/z 831 (Mϩ ϩ 23, 2.4%), 226 (6.8), 91 (84),
87 (24), 73 (100) and 59 (17).
(1R,2R,3R,4R,8S,9S)-2,3-Bis[(trimethylsilylethoxymethyl)-
oxy]-8,9-bis(benzyloxy)cyclododeca-6,10-diyne-1,4-diol (؉)-21
K2CO3 (34.0 mg, 0.25 mmol) was added to a solution of 20
(56.0 mg, 0.06 mmol) in MeOH (4.0 cm3) and the mixture
was stirred at rt for 12 h. MeOH was evaporated off and the
residue was taken up in AcOEt, which was washed with sat-
urated aq. NH4Cl, water and brine, dried and concentrated to
dryness. Chromatography of the residue with hexane–AcOEt
(4:1) afforded (ϩ)-21 (38.0 mg, 87%) as a colorless oil
(Found: C, 65.2; H, 8.2. C38H56O8Si2 requires C, 65.5; H,
(3S,4S)-6-(tert-Butyldimethylsiloxy)-3,4-bis(methoxy)hexan-1-
ol (؊)-27
8.1%); [α]D27 ϩ10.2 (c 0.51, CHCl3); νmax/cmϪ1 3523 (OH) and
᎐
2220 (C᎐C); δ 7.37–7.26 (10H, m, aromatic H), 4.94, 4.79
᎐
H
(4H, AB-q, J 6.8, OCH2O), 4.76, 4.59 (4H, AB-q, J 12.2,
benzylic H), 4.43 (2H, d, J 3.9, 2-H and 3-H), 4.36 (2H, s,
8-H and 9-H), 4.26 (2H, m, 1-H and 4-H), 3.75–3.69 (4H, m,
TMSCH2CH2), 3.52 (2H, d, J 7.8, OH), 2.80 (2H, dd, J 16.6
and 5.4, 5-H and 12-H), 2.56 (2H, dd, J 16.6 and 9.8, 5-H
A solution of 26 (1.99 g, 11.4 mmol) in THF (10.0 cm3) was
added to a suspension of NaH (303 mg, 12.6 mmol) in THF
(30.0 cm3) at 0 ЊC. The THF solution was stirred for 1 h, to
which a solution of TBDMSCl (1.90 g, 12.6 mmol) in THF
(10.0 ml) was added. After stirring for 3 h, the reaction mixture
J. Chem. Soc., Perkin Trans. 1, 2000, 737–744
741