42
A. Miyachi et al. / Carbohydrate Research 344 (2009) 36–43
4.12. 3-O-[(200,300-Di-O-benzyl-400,600-O-benzylidene-b-
galactopyranosyl)-(1?6)-(20,30,40-tri-O- benzyl-b-
galactopyranosyl)]-1,2-di-O-palmitoyl-sn-glycerol (15)
D-
ꢀOCOCH2–), 1.61 (m, 4H, ꢀOCOCH2CH2–), 1.27 (b, 48H, –OCOCH2-
CH2(CH2)12–), 0.88 (t ꢃ 2, 6H, –CH2CH3); 13C NMR (125 MHz,
CDCl3–CD3OD = 10:1): d 174.12, 173.88, 103.98, 103.61, 74.99,
73.55, 73.26, 73.11, 71.28, 70.33, 69.16, 68.07, 67.77, 67.41,
62.83, 61.77, 34.40, 34.24, 32.03, 29.81, 29.77, 29.63, 29.47,
29.42, 29.25, 29.22, 25.00, 24.98, 22.79, 14.16; HRFABMS: m/z calcd
for C47H88O15Na [M+Na]+ 915.6021; found: 915.5977.
D-
To a solution of compound 14 (30 mg, 25.1
of CH2Cl2 (1.0 mL), 2-PrOH (500 L), and H2O (500
DDQ (15.2 mg, 60.2 mol) at 0 °C, and the mixture was stirred at
lmol) in a mixture
l
lL) was added
l
rt for 5 h. To the reaction mixture was added satd NaHCO3, fol-
lowed by washing with brine. The organic extract was dried over
MgSO4, and concentrated under diminished pressure. The residue
4.14. 3-O-[(200,300,400,600-Tetra-O-benzyl-b-
(1?6)-(20,30,40-tri-O-benzyl-b-
- galactopyranosyl)]-1,2-di-O-(4-
D-glucopyranosyl)-
D
was dissolved in pyridine (500
lL), and to the solution was added
methoxybenzyl)-sn-glycerol (16)
a solution of palmitoyl chloride (22.5
l
L, 75.3 mol) in CH2Cl2
l
(1.0 mL) at 0 °C. After stirring at rt for 15 h, the reaction was
quenched by addition of MeOH at 0 °C, and the mixture was ex-
tracted with toluene. The organic layer was washed with satd NaH-
CO3 and satd brine, dried over MgSO4, and concentrated under
diminished pressure. The residue was purified by chromatography
(silica gel, 15:1 toluene–EtOAc) to give diacylglycerogalactoside 15
A suspension of flame-dried 3 Å MS (50 mg), thioglucoside do-
nor 4 (59.3 mg, 85.8
68.5 mol) in dry CH2Cl2 (1.0 mL) and dry acetonitrile (1.0 mL)
was stirred at rt for 3 h. To the reaction mixture was added NIS
(24.1 mg, 107
mol) at rt, followed by cooling to ꢀ40 °C. As soon
as the reaction mixture was cooled, to the mixture was added TfOH
(2.0 L), and the reaction mixture was stirred at that temperature
lmol), and acceptor alcohol 13 (52.4 mg,
l
l
(28.7 mg, 80%) as a colorless amorphous solid: ½a D30
ꢂ
+11.5 (c 0.954,
l
CHCl3); 1H NMR (500 MHz, CDCl3): d 7.20–7.54 (m, 30H, Ar), 5.49
(s, 1H, ArCH), 5.12 (m, 1H, H-2), 4.60-4.93 (d ꢃ 10, 10H, ArCH2),
for 15 min. The reaction was quenched by addition of Et3N, and the
mixture was filtered through a pad of Celite. The filtrate was
washed with 5% aq Na2S2O3, satd NaHCO3, and brine, dried over
MgSO4, and concentrated under diminished pressure. The residue
was purified by chromatography (silica gel, 10:1 toluene–EtOAc)
to give glycosylated product 16 (60.8 mg, 69%) as a colorless syrup:
4.45 (d, 1H, J1 ,2 7.5 Hz, H-100), 4.25 (dd, 1H, J1,1 12.0 Hz, J1,2 3.5
00 00
Hz, H-1), 4.23 (d, 1H, J1 ,2 8.0 Hz, H-10), 4.23 (dd, 1H, J5 ,6 1.5 Hz,
0
0
00 00
J6 ,6 11.5 Hz, H-600), 4.13 (dd, 1H, J1,1 12.0 Hz, J1,2 7.0 Hz, H-1),
00 00
4.12 (bd, 1H, J3 ,4 3.0 Hz, H-400), 4.00 (dd, 1H, J5 ,6 2.0 Hz, J6 ,6
11.5 Hz, H-600), 3.91 (dd, 1H, J2,3 5.0 Hz, J3,3 11.0 Hz, H-3), 3.90
00 00
00 00
00 00
½
a 3D0
ꢂ
+5.16 (c 1.440, CHCl3); 1H NMR (500 MHz, CDCl3): d 6.75–7.36
(dd, 1H, J5 ,6 5.0 Hz, J6 ,6 11.0 Hz, H-60), 3.74-3.79 (m, 4H, H-200,
(m, 39H, Ar), 4.39–4.93 (d ꢃ 18, 18H, ArCH2), 4.43 (d, 1H, J1 ,2
0
0
0
0
00 00
H-20, H-40, H-60), 3.55 (dd, 1H, J2 ,3 9.5 Hz, J3 ,4 3.5 Hz, H-300),
7.7 Hz, H-100), 4.31 (d, 1H, J1 ,2 7.4 Hz, H-10), 3.96 (dd, 1H, J5 ,6
00 00
00 00
0
0
0
0
3.50 (m, 1H, H-50), 3.47 (dd, 1H, J2,3 5.0 Hz, J3,3 11.0 Hz, H-3), 3.44
4.5 Hz, J6 ,6 10.4 Hz, H-60), 3.88 (dd, 1H, J5 ,6 5.4 Hz, J6 ,6 10.4 Hz,
H-60), 3.74 and 3.72 (s ꢃ 2, 6H, Me), 3.52-3.81 (m, 11H, H-1 ꢃ 2,
H-2, H-3 ꢃ 2, H-40, H-200, H-300, H-400, H-600 ꢃ 2), 3.49 (m, 1H, H-50),
0
0
0
0
0
0
(dd, 1H, J2 ,3 10.0 Hz, J3 ,4 3.0 Hz, H-30), 3.31 (ddd, 1H, J4 ,5 0.5 Hz,
0
0
0
0
00 00
J5 ,6 1.5 Hz,2.0 Hz, H-500), 2.34 and 2.23 (t ꢃ 2, 4 H, –OCOCH2–),
00 00
3.44 (dd, 1H, J2 ,3 9.9 Hz, J3 ,4 2.9 Hz, H-30), 3.36-3.41 (m, 2H, H-
20, H-500); 13C NMR (125 MHz, CDCl3): d 159.01, 158.96, 138.72,
138.55, 138.51, 138.46, 138.15, 138.05, 130.77, 130.47, 129.19,
129.12, 128.40, 128.33, 128.30, 128.17, 128.04, 127.86, 127.81,
127.75, 127.67, 127.58, 127.56, 127.52, 127.48, 127.39, 113.65,
113.60, 104.16, 103.61, 84.67, 82.15, 81.97, 79.33, 77.65, 75.63,
74.97, 74.92, 74.67, 74.55, 74.38, 73.82, 73.58, 73.43, 73.08,
72.83, 71.54, 70.30, 69.07, 68.71, 68.40, 55.16; HRFABMS: m/z calcd
for C80H86O15K [M+K]+ 1325.5604; found: 1325.5701.
0
0
0
0
1.63 (m, 4H, –OCOCH2CH2–), 1.25 (b, 48H, –COCH2CH2(CH2)12–),
0.88 (t ꢃ 2, 6H, –CH2CH3); 13C NMR (100 MHz, CDCl3): d 173.35,
173.02, 139.01, 138.68, 138.43, 137.90, 128.92, 128.53, 128.39,
128.36, 128.31, 128.28, 128.24, 128.14, 128.10, 127.78, 127.74,
127.69, 127.62, 127.58, 127.55, 127.52, 126.48, 104.18, 103.51,
101.29, 81.94, 79.30, 79.09, 78.49, 77.26, 75.05, 74.45, 74.17,
73.92, 73.46, 73.17, 72.00, 69.97, 69.18, 68.13, 67.92, 66.40,
62.86, 34.29, 34.13, 31.97, 29.75, 29.73, 29.70, 29.64, 29.56,
29.41, 29.37, 29.35, 29.20, 29.15, 24.93, 24.90, 22.74, 14.17; MAL-
DI-TOFMS m/z calcd for C89H122O15Na [M+Na]+ 1454; found: 1454.
4.15. 3-O-[(200,300,400,600-Tetra-O-benzyl-b-
D
-glucopyranosyl)-
4.13. 3-O-[b-
D-Galactopyranosyl-(1?6)-b-
D-galactopyranosyl]-
(1?6)-(20,30,40-tri-O-benzyl-b-
palmitoyl-sn-glycerol (17)
D- galactopyranosyl)]-1,2-di-O-
1,2-di-O-palmitoyl-sn-glycerol (1)
To a solution of benzyl ether 15 (55 mg, 38
l
mol) in a mixture
To a solution of compound 16 (29 mg, 22.5
of CH2Cl2 (1.0 mL), 2-PrOH (500 L) and H2O (500
DDQ (13.6 mg, 53.7 mol) at 0 °C, and the mixture was stirred at
rt for 5 h. To the reaction mixture was added satd NaHCO3, and
the organic extract was then washed with brine, dried over MgSO4,
and concentrated under diminished pressure. The residue was dis-
l
mol) in a mixture
of THF (1.5 mL) and MeOH (10 mL) was added 10% Pd/C (catalytic
amount). (Caution! Extreme fire hazard!) The reaction mixture
was stirred vigorously under an H2 atmosphere at rt for 8 h. The
reaction mixture was filtered through a glass filter, and the filtrate
was concentrated under diminished pressure, and the residue was
purified by chromatography (Iatrobeads, 10:1 CHCl3–MeOH) to
l
l
L) was added
l
solved in pyridine (500
lL), and to the solution was added a solu-
give 1 (27 mg, 88%) as a white crystal: ½a D24
ꢂ
ꢀ0.82 (c 0.1, 2:1
tion of palmitoyl chloride (20.3
l
L, 67.2 mol) in CH2Cl2 (1.0 mL)
l
CHCl3–MeOH); IR (film):
m
3415, 1733, 1070 cmꢀ1
;
1H NMR
at 0 °C. After stirring at rt for 18 h, the reaction was quenched by
addition of MeOH at 0 °C, followed by extraction with toluene.
The organic layer was washed with satd NaHCO3 and satd brine,
dried over MgSO4, and concentrated under diminished pressure.
The residue was purified by chromatography (silica gel, 15:1 tolu-
ene–EtOAc) to give diacylglycerogalactoside 17 (28.5 mg, 83%
(500 MHz, CDCl3–CD3OD = 4:1): d 5.25 (m, 1H, H-2), 4.37 (dd, 1H,
J1,1 12.0 Hz, J1,2 3.5 Hz, H-1), 4.30 (d, 1H, J1 ,2 7.5 Hz, H-100), 4.23
00 00
0
0
(dd, 1H, J1,1 11.5 Hz, J1,2 6.5 Hz, H-1), 4.22 (d, 1H, J1 ,2 7.0 Hz, H-
10), 4.03 (dd, 1H, J5 ,6 6.5 Hz, J6 ,6 10.5 Hz, H-60), 3.97 (br d, 1H,
0
0
0
0
J3 ,4 3.0 Hz, H-40), 3.91 (dd, 1H, J2,3 5.5 Hz, J3,3 11.0 Hz, H-3), 3.88
0
0
(br d, 1H, J3 ,4 4.0 Hz, H-400), 3.86 (dd, 1H, J5 ,6 6.0 Hz, J6 ,6
2 steps) as a colorless amorphous solid: ½a D27
ꢂ
+5.49 (c 0.760, CHCl3);
00 00
0
0
0
0
11.0 Hz, H-60), 3.84 (dd, 1H, J5 ,6 7.0 Hz, J6 ,6 11.5 Hz, H-600), 3.76
1H NMR (500 MHz, CDCl3): d 7.13–7.36 (m, 35H, Ar), 5.13 (m, 1H,
00 00
00 00
(dd, 1H, J5 ,6 5.0 Hz, J6 ,6 12.0 Hz, H-600), 3.73 (dd, 1H, J2,3 5.5 Hz,
H-2), 4.45–4.92 (d ꢃ 14, 14H, ArCH2), 4.41 (d, 1H, J1 ,2 7.5 Hz, H-
00 00
00 00
00 00
J3,3 11.0 Hz, H-3), 3.67 (m, 1H, H-50), 3.56 (dd, 1H, J1 ,2 7.5 Hz, J2 ,3
100), 4.26 (d, 1H, J1 ,2 7.5 Hz, H-10), 4.25 (dd, 1H, J1,1 12.5 Hz, J1,2
3.0 Hz, H-1), 4.12 (dd, 1H, J1,1 12.5 Hz, J1,2 6.5 Hz, H-1), 3.93 (dd,
00 00
00 00
0
0
9.5 Hz, H-200), 3.54 (dd, 1H, J1 ,2 7.5 Hz, J2 ,3 9.5 Hz, H-20), 3.53 (m,
0
0
0
0
1H, H-500), 3.50 (dd, 1H, J2 ,3 9.5 Hz, J3 ,4 3.5 Hz, H-30), 3.49 (dd,
1H, J2,3 4.0 Hz, J3,3 11.0 Hz, H-3), 3.87 (dd, 1H, J5 ,6 5.0 Hz, J6 ,6
0
0
0
0
0
0
0
0
1H, J2 ,3 9.5 Hz, J3 ,4 4.0 Hz, H-300), 2.32 and 2.30 (t ꢃ 2, 4H,
11.0 Hz, H-60), 3.75-3.80 (m, 3H, H-20, H-40, H-60), 3.68 (m, 2H,
00 00
00 00