K. Yamamoto et al. / Carbohydrate Research 345 (2010) 572–585
579
gave 2,3,4-O-tri-(4-methoxyphenylmethyl)-6-O-triphenylmethyl-
b- -galactopyranosyl-(1?4)-1-O-(tert-butyldimethylsilyl)-2,3-di-O-
(C1), 113.33, 113.46, 113.52, 113.62, 113.67, 126.96, 126.98,
127.80, 127.82, 128.61, 128.66, 128.79, 129.43, 129.49, 129.60,
129.69, 130.31, 130.49, 130.77, 130.86, 131.14, 143.70, 143.77,
158.87, 158.88, 158.90, 158.97, 158.98 (aromatic carbons), 205.74
(C20); ESIMS (%, rel. int.) m/z: 1563.7013 (55, calcd for C96H104O16S-
iNa [M+Na]+: 1563.6991), 1558.7428 (91, calcd for C96H108NO16Si
[M+NH4]+: 1558.7437).
D
(4-methoxyphenylmethyl)-6-O-triphenylmethyl-
D
-galactitol (1.57 g,
+24.5 (c 1.15, CHCl3); IR (film) 3465, 2930,
1H NMR (500 MHz,
98%) as an oil: ½a D25
ꢃ
1610, 1510, 1250, 1080, 1035, 830, 705 cmꢀ1
;
CDCl3) d ꢀ0.07, ꢀ0.05 (each 3H, s, SiCH3), 0.81 (9H, s, SiC(CH3)3),
2.93 (dd, 1H, J = 3.3, 10.0 Hz, C60HH), 3.02 (t, 1H, J = 8.7 Hz,
C6HH), 3.21 (dd, 1H, J = 5.0, 8.7 Hz, C6HH), 3.36 (dd, 1H, J = 6.0,
10.0 Hz, C60HH), 3.49 (2H, C20H, C30H), 3.69, 3.71 (each s, 3H,
OCH3), 3.76–3.79 (10H, C10HH, OCH3 ꢂ 3), 3.87–3.91 (3H, C10HH,
C2H, C3H), 4.11 (2H, C4H, C50H), 4.17, 4.24 (each d, 1H,
J = 11.1 Hz, ArCHHO), 4.25–4.31 (3H, C40H, C5H, ArCHHO), 4.35
(d, 1H, J = 12.3 Hz, ArCHHO), 4.41 (d, 1H, J = 3.3 Hz, C50OH), 4.44
(d, 1H, J = 12.3 Hz, ArCHHO), 4.52 (d, 1H, J = 11.3 Hz, ArCHHO),
4.60, 4.63 (each d, 1H, J = 11.4 Hz, ArCHHO), 4.67 (d, 1H,
J = 10.4 Hz, ArCHHO), 4.71 (d, 1H, J = 11.3 Hz, ArCHHO), 4.90 (d,
1H, J = 2.8 Hz, C1H), 6.62 (br d, 2H, J = 8.7 Hz, aromatic protons),
6.71 (br d, 2H, J = 8.7 Hz, aromatic protons), 6.75 (br d, 2H,
J = 8.7 Hz, aromatic protons), 6.76 (br d, 2H, J = 8.7 Hz, aromatic pro-
tons), 6.88 (br d, 2H, J = 8.6 Hz, aromatic protons), 6.96 (4H, aromatic
protons), 7.02 (br d, 2H, J = 8.7 Hz, aromatic protons), 7.14–7.32
(28H, aromatic protons), 7.42 (6H, aromatic protons); 13C NMR
A solution of the product (2.00 g, 1.30 mmol) in a mixture of tol-
uene (30 mL) and pyridine (0.5 mL) was stirred with the second-
generation Tebbe reagent17 (0.5 M in toluene, 7.8 mL, 3.90 mmol)
at ꢀ40 °C for 15 min. The ice bath was removed, and the mixture
was further stirred at ambient temperature for 1 h. After 1.0 M
aq NaOH (2.0 mL) was added to quench the reaction at 0 °C, the
mixture was filtered through Celite, and the filtrate was concen-
trated in vacuo. Purification of the residue with silica gel column
chromatography (18:82 EtOAc–hexane) gave 11 (1.30 g, 65%) as
an oil. ½a 2D4
ꢃ
+45.3 (c 1.00, CHCl3); IR (film) 2925, 1610, 1510,
1250, 1090, 1035, 830, 705 cmꢀ1
;
1H NMR (500 MHz, CDCl3) d
ꢀ0.21, ꢀ0.20 (each 3H, s, SiCH3), 0.71 (9H, s, SiC(CH3)3), 3.07 (dd,
1H, J = 7.0, 8.7 Hz, C6HH), 3.38 (dd, 1H, J = 6.1, 8.7 Hz, C6HH),
3.39–3.45 (3H, C60H2, C50H), 3.48 (t, 1H, J = 3.8 Hz, C40H), 3.71 (s,
3H, OCH3), 3.73–3.77 (14H, C20H2, OCH3 ꢂ 4), 3.90 (2H, C3H,
C4H), 3.95 (dd, 1H, J = 3.4, 10.5 Hz, C2H), 4.18 (br dd, 1H, J = 6.1,
7.0 Hz, C5H), 4.30 (d, 1H, J = 12.0 Hz, ArCHHO), 4.31 (d, 1H,
J = 11.2 Hz, ArCHHO), 4.41–4.51 (5H, ArCHHO ꢂ 5), 4.54 (d, 1H,
J = 11.5 Hz, ArCHHO), 4.56 (d, 1H, J = 3.8 Hz, C30H), 4.66 (d, 1H,
J = 11.5 Hz, ArCHHO), 4.72 (d, 1H, J = 10.8 Hz, ArCHHO), 5.00 (d,
1H, J = 3.4 Hz, C1H), 5.50, 5.71 (each br s, 1H, C10H), 6.64 (br d,
2H, J = 8.7 Hz, aromatic protons), 6.67 (br d, 2H, J = 8.6 Hz, aromatic
protons), 6.69 (br d, 2H, J = 8.7 Hz, aromatic protons), 6.78 (br d, 2H,
J = 8.7 Hz, aromatic protons), 6.80 (br d, 2H, J = 8.6 Hz, aromatic pro-
tons), 6.95 (br d, 2H, J = 8.7 Hz, aromatic protons), 6.97 (br d, 2H,
J = 8.7 Hz, aromatic protons), 7.07 (br d, 2H, J = 8.7 Hz, aromatic pro-
tons), 7.14–7.23 (22H, aromatic protons), 7.35–7.38 (12H, aromatic
protons); 13C NMR (125 MHz, CDCl3) d ꢀ5.50, ꢀ5.40 (each SiCH3),
18.04 (SiC), 25.84 (SiC(CH3)3), 55.10, 55.16, 55.17, 55.19, 55.21
(each OCH3), 62.86 (C6), 63.36 (C60), 64.51 (C20CH2), 70.12 (C5),
72.49, 72.53, 72.57, 72.87, 74.03 (each ArCH2O), 75.44 (C4), 75.86
(C2), 76.68 (C30), 77.68 (C40), 78.57 (C3), 78.71 (C50), 86.58, 86.84
(each CPh3), 94.31 (C1), 113.35 (ꢂ2), 113.39, 113.52, 113.60 (aro-
matic carbons), 115.10 (C10), 126.88, 126.91, 127.76 (ꢂ2), 128.59,
128.73, 128.80, 129.41, 129.48, 129.54, 129.79, 130.67, 130.91,
131.00, 131.18, 131.47 (aromatic carbons), 143.23 (C20), 143.83,
144.25, 158.77, 158.79, 158.83, 158.88, 158.90 (aromatic carbons);
ESIMS (%, rel. int.) m/z: 1561.7184 (43, calcd for C97H106O15SiNa
[M+Na]+: 1561.7199), 1556.7620 (88, calcd for C97H110NO15Si
[M+NH4]+: 1556.7645).
(125 MHz, CDCl3)
d
ꢀ5.27 (SiCH3 ꢂ 2), 18.25 (SiC), 25.98
(SiC(CH3)3), 55.12 (OCH3 ꢂ 2), 55.21 (OCH3), 55.22 (OCH3 ꢂ 2),
61.47 (C6), 64.09 (C10), 64.46 (C60), 70.25 (C5), 70.38 (C50), 71.59,
72.10, 72.89, 73.86, 74.27 (each ArCH2O), 74.75 (C4), 75.57 (C2),
76.87 (C30), 79.44 (C3), 81.18 (C40), 81.62 (C20), 86.26, 86.66 (each
CPh3), 101.88 (C1), 113.32, 113.41, 113.49, 113.71, 113.72,
126.83, 126.94, 127.76, 127.79, 128.61, 128.67, 128.76, 128.99,
129.01, 129.42, 129.85, 130.25, 130.57, 130.92, 131.04, 131.06,
143.75, 144.24, 158.75, 158.77, 158.84, 159.00, 159.25 (aromatic
carbons); ESIMS (%, rel. int.) m/z: 1565.7178 (41, calcd for
C96H106O16SiNa [M+Na]+: 1565.7148).
A solution of the product thus obtained (1.24 g, 803 lmol) in a
mixture of DMSO (30 mL, 418 mmol) and Ac2O (15 mL, 160 mmol)
was stirred at room temperature for 10 h. The mixture was poured
into H2O (300 mL), and the aqueous layer was extracted with
EtOAc (150 mL ꢂ 3). The organic layers were washed with H2O
(100 mL) and brine (100 mL) successively, combined, dried over
MgSO4, and then concentrated in vacuo. Silica gel column chroma-
tography (18:82 EtOAc–hexane) of the residue afforded (3S,4S,5S)-
6-(tert-butyldimethylsilyloxy)-4,5-di-(4-methoxyphenylmethoxy)-
1-triphenylmethoxy-2-hexanon-3-yl 2,3,5-O-tri-(4-methoxyphe-
nylmethyl)-6-O-triphenyl methyl-
a
-
D
-galactopyranoside (1.23 g,
+21.2 (c 1.78, CHCl3); IR (film) 2930, 1730,
1H NMR (500 MHz,
99%) as an oil: ½a D25
ꢃ
1610, 1510, 1250, 1090, 1035, 830, 705 cmꢀ1
;
CDCl3) d ꢀ0.11, ꢀ0.09 (each 3H, s, SiCH3), 0.80 (9H, s, SiC(CH3)3),
2.94 (t, 1H, J = 7.8 Hz, C6HH), 3.27 (dd, 1H, J = 5.8, 7.8 Hz, C6HH),
3.59 (1H, C50H), 3.65 (dd, 1H, J = 2.8, 10.2 Hz, C3H), 3.73–3.78
(18H, C60H2, C2H, OCH3 ꢂ 5), 3.81 (br d, 1H, J = 2.8 Hz, C4H), 3.86
(dd, 1H, J = 3.4, 5.8 Hz, C40H), 3.97 (dd, 1H, J = 5.8, 7.8 Hz, C5H),
4.19 (d, 1H, J = 18.2 Hz, C10HH), 4.24 (d, 1H, J = 10.7 Hz, ArCHHO),
4.25 (d, 1H, J = 11.8 Hz, ArCHHO), 4.39 (d, 1H, J = 11.8 Hz, ArCHHO),
4.40 (s, 2H, ArCH2O), 4.41 (d, 1H, J = 18.2 Hz, C10HH), 4.44, 4.49
(each d, 1H, J = 11.6 Hz, ArCHHO), 4.50 (d, 1H, J = 11.2 Hz, ArCHHO),
4.61 (d, 1H, J = 3.2 Hz, C1H), 4.62 (d, 1H, J = 10.7 Hz, ArCHHO), 4.65
(d, 1H, J = 11.2 Hz, ArCHHO), 6.67 (4H, aromatic protons), 6.74 (4H,
aromatic protons), 6.88 (4H, aromatic protons), 6.96 (br d, 2H,
J = 8.6 Hz, aromatic protons), 7.06 (br d, 2H, J = 8.6 Hz, aromatic pro-
tons), 7.13–7.26 (22H, aromatic protons), 7.31 (6H, aromatic pro-
tons), 7.42 (6H, aromatic protons); 13C NMR (125 MHz, CDCl3) d
ꢀ5.40, ꢀ5.38 (each SiCH3), 18.17 (SiC), 25.94 (SiC(CH3)3), 55.14,
55.15 (each OCH3), 55.17 (OCH3 ꢂ 2), 55.21 (OCH3), 62.35 (C6),
63.33 (C60), 69.98 (C10), 70.52 (C5), 71.92, 72.78, 72.95, 73.27,
74.10 (each ArCH2O), 74.74 (C2), 75.17 (C4), 78.69 (C3), 80.08
(C40), 80.69 (C50), 82.01 (C30), 86.61, 86.89 (each CPh3), 98.61
3.10. (3RS,4R,5S,6S)-4,5-Di-(4-methoxyphenylmethoxy)-3-
hydroxy-7-(triphenylmethoxymethyl)octa-1,7-dien-6-yl 2,3,4-
tri-O-(4-methoxyphenylmethyl)-6-O-triphenylmethyl-a-D-
galactopyranoside (12)
A solution of 11 (475 mg, 0.31 mmol) in THF (6.0 mL) was stir-
red with tetrabutylammonium fluoride (1.0 M in THF, 0.47 mL) at
room temperature for 2 h. The mixture was poured into H2O
(50 mL), and the aqueous layer was extracted with EtOAc
(50 mL ꢂ 3). The combined organic layer was washed with brine
(50 mL), dried over MgSO4, and then concentrated in vacuo. Purifi-
cation of the residue with silica gel column chromatography (26:74
EtOAc–hexane) gave the corresponding alcohol (422 mg, 97%) as
an oil: ½a 2D4
ꢃ
+46.5 (c 1.00, CHCl3); IR (film) 3500, 2930, 1610,
1510, 1250, 1090, 1035, 820, 705 cmꢀ1; 1H NMR (500 MHz, CDCl3)
d 1.85 (dd, 1H, J = 4.8, 7.0 Hz, C60OH), 2.99 (dd, 1H, J = 6.2, 9.0 Hz,
C6HH), 3.35–3.44 (3H, C6HH, C50H, C60HH), 3.51 (ddd, 1H, J = 3.7,
7.0, 11.3 Hz, C60HH), 3.59 (dd, 1H, J = 4.2, 6.6 Hz, C40H), 3.736 (s,