4768
Z. Pakulski, P. Cmoch / Tetrahedron 71 (2015) 4757e4769
using the procedure described for 7. Column chromatography of the
crude product (hexaneeethyl acetate, 40:1/5:1; all eluents con-
tained 0.5% Et3N) afforded 59 (220 mg, 51%) and a mixture of 59 and
Data for 64: 1H NMR (CDCl3)
d: selected signalsd6.08 (dq, 1H,
J 1.4, 12.3 Hz, OCH¼), 5.00e5.05 (m, 2H, H-10,¼CH), 4.96 (dd, 1H,
J2,1 5.9, J2,3 6.7 Hz, H-2), 4.89 (dd, 1H, J2,1 2,7, J2,3 7.8 Hz, H-20),
4.63 (d, 1H, J1,2 5.9 Hz, H-1), 4.11e4.15 (m, 1H, H-5), 4.08 (dd, 1H,
J3,2 7.8, J3,4 3.0 Hz, H-30), 3.88e3.90 (m, 1H, H-40), 3.87 (s, 3H,
OCH3), 3.74e3.77 (m, 1H, H-3), 3.65e3.68 (m, 1H, H-4),
60 (102 mg, 24%).
20
Data for 59: [
a
]
52.7 (c 0.3, chloroform); 1H NMR (CDCl3)
d:
D
8.01e8.02 (m, 2H, Ar), 6.89e6.91 (m, 2H, Ar), 5.83e5.89 (m, 1H,
CH¼), 5.23e5.26 (m, 1H,¼CHH), 5.16e5.17 (m, 1H,¼CHH), 5.10 (dd,
1H, J2,1 2.2, J2,3 6.5 Hz, H-2), 4.97 (dd, 1H, J2,1 5.9, J2,3 7.2 Hz, H-20),
4.84 (br s, 1H, H-1), 4.80 (d, 1H, J1,2 5.9 Hz, H-10), 4.18e4.21 (m, 1H,
3.60e3.61 (m, 1H, H-50, H-50), 3.24 (dd, 1H, J5,4 7.5, J5,5 11.7 Hz, H-
0
5), 2.09 (s, 3H, CH3). 13C NMR (CDCl3)
d: selected signalsd104.3
(¼CH), 99.2 (C-1), 96.1 (C-10), 74.0 (C-40), 73.8 (C-3), 73.0 (C-2),
71.4 (C-20), 71.0 (C-4), 68.1 (C-30), 64.7 (C-5), 60.6 (C-50), 55.4,
21.0. Anal. Calcd for C41H72O12Si3 (841.28): C, 58.54; H, 8.63.
Found: C, 58.74; H, 8.63.
0
0
OCHH), 4.05 (dd, 1H, J5,4 4.1, J5,5 11.7 Hz, H-5 ), 3.98e4.01 (m, 2H, H-
3, OCHH), 3.92e3.94 (m, 1H, H-4), 3.87 (s, 3H, OCH3), 3.73 (t, 1H,
J3,2¼J3,4¼7.2 Hz, H-30), 3.66e3.69 (m, 1H, H-40), 3.47 (dd, 1H, J5,4 3.2,
0
0
J5,5 11.3 Hz, H-5), 3.38 (dd,1H, J5,4 7.4, J5,5 11.3 Hz, H-5), 3.24 (dd,1H,
J5,4 7.8, J5,5 11.7 Hz, H-50), 2.10 (s, 3H, CH3), 0.86e0.96 (m, 27H,
5.2.32. Allyl 2-O-(4-methoxybenzoyl)-
b-L-xylopyranosyl-(1/3)-2-
0
9ꢂCH3), 0.50e0.63 (m, 18H, 9ꢂCH2). 13C NMR (CDCl3)
d
: 169.9,
O-acetyl- -arabinopyranoside (65). Desilylation of 59 (84 mg,
b-L
164.9, 163.3, 133.8, 131.8, 122.8, 117.2, 113.4, 100.5 (C-10), 96.0 (C-1),
74.0 (C-30), 73.6 (C-3), 73.4 (C-20), 71.1 (C-40), 70.7 (C-2), 69.3
(CH2O), 66.9 (C-4), 64.7 (C-50), 63.9 (C-5), 55.4, 21.0, 6.8, 6.7, 5.0, 4.9,
4.7. Anal. Calcd for C41H72O12Si3 (841.28): C, 58.54; H, 8.63. Found:
C, 58.44; H, 8.68.
0.10 mmol) was performed using the procedure described for 51.
Column chromatography of the crude product (hexaneeethyl
20
acetate, 10:1/1:1) afforded 65 (43 mg, 86%). [
a
]
101.2 (c 0.3,
D
chloroform); nmax (film): 3444 (br), 2928, 2872, 1716, 1604, 1256,
1171, 1141, 1098, 1065, 1030, 848, 768 cmꢁ1 1H NMR (CDCl3)
.
d:
Data for 60: 1H NMR (CDCl3)
d
: 8.00e8.02 (m, 2H, Ar), 6.89e6.92
7.93e7.95 (m, 2H, Ar), 6.88e6.89 (m, 2H, Ar), 5.82e5.90 (m, 1H,
CH¼), 5.26e5.30 (m, 1H,¼CHH), 5.18e5.20 (m, 2H, H-2,¼CHH),
4.98 (d, 1H, J1,2 3.5 Hz, H-1), 4.94 (dd, 1H, J2,1 5.7, J2,3 7.3 Hz, H-2),
4.08e4.17 (m, 3H), 3.97e4.00 (m, 1H, OCHH), 3.90e3.92 (m, 1H,
H-4), 3.84 (s, 3H, OCH3), 3.73e3.78 (m, 3H), 3.66 (dd, 1H, J5,4 2.3,
(m, 2H, Ar), 5.78e5.86 (m, 1H, CH¼), 5.20e5.24 (m, 1H,¼CHH),
5.12e5.14 (m, 1H,¼CHH), 4.96 (dd, 1H, J2,1 6.0, J2,3 7.0 Hz, H-2),
4.85e4.87 (m, 2H, H-1, H-20), 4.62 (d, 1H, J1,2 5.7 Hz, H-10), 4.14e4.18
0
(m, 1H, OCHH), 4.11 (dd, 1H, J5,4 2.9, J5,5 11.7 Hz, H-5), 4.07 (dd, 1H,
J3,2 6.4, J3,4 2.9 Hz, H-30), 3.92e3.96 (m, 1H, OCHH), 3.88e3.90 (m,
J5,5 12.5 Hz, H-5), 3.40 (dd, 1H, J5,4 7.5, J5,5 11.8 Hz, H-5), 2.08 (s,
0
0
1H, H-40), 3.87 (s, 3H, OCH3), 3.75 (t, 1H, J3,2¼J3,4¼7.0 Hz0, H-3),
3H, CH3). 13C NMR (CDCl3)
d
: 170.6, 166.1, 164.0, 133.6, 131.9,
0
3.64e3.68 (m, 1H, H-4), 3.62 (dd, 1H, J5,4 3.1, J5,5 11.7 Hz, H-5 ), 5.57
121.2, 117.7, 113.9, 99.3, 95.8, 75.1, 73.7, 73.4, 69.4, 69.1, 68.4,
66.9, 64.1, 61.9, 55.5, 21.0. HRMS (ESI) calcd for C23H30NaO12
[MþNa]þ: 521.1635. Found: 521.1644. Anal. Calcd for
(dd, 1H, J5,4 6.3, J6,6 11.7 Hz, H-50), 3.23 (dd, 1H, J5,4 7.7, J5,5 11.7 Hz,
H-5), 2.10 (s, 3H, CH3), 0.96 (t, 9H, J 7.9 Hz, CH3), 0.92 (t, 9H, J 7.9 Hz,
CH3), 0.88 (t, 9H, J 7.9 Hz, CH3), 0.52e0.64 (m, 18H, CH2). 13C NMR
0
0
C
23H30O12ꢂ½H2O (507.50): C, 54.43; H, 6.16. Found: C, 54.77; H,
(CDCl3)
d: 170.1, 164.7, 163.3, 134.0, 131.8, 122.8, 116.9, 113.4, 99.5,
6.35.
95.7, 74.0, 73.0, 72.0, 71.1, 68.9, 68.3, 64.8, 60.4, 55.4, 21.0, 6.8, 6.7,
5.0, 5.0, 4.7. Anal. Calcd for C41H72O12Si3 (841.28): C, 58.54; H, 8.63.
Found: C, 58.31; H, 8.60.
5.2.33. Allyl 3,4-di-O-acetyl-2-O-(4-methoxybenzoyl)-b-L-xylopyr-
anosyl-(1/3)-2,4-di-O-acetyl-b-L-arabinopyranoside (66). Triol 65
(43 mg, 0.086 mmol) was acetylated under standard conditions
(Ac2O, pyridine). Column chromatography of the crude reaction
5.2.31. (E,Z)-1-Propenyl
thylsilyl- -xylopyranosyl-(1/3)-2-O-acetyl-4-O-triethylsilyl-
arabinopyranoside (63) and (E,Z)-1-propenyl 2-O-(4-
methoxybenzoyl)-3,4-di-O-triethylsilyl- -xylopyranosyl-(1/4)-2-
O-acetyl-3-O-triethylsilyl- -arabinopyranoside (64). Method A. A
2-O-(4-methoxybenzoyl)-3,4-di-O-trie-
b
-
L
b
-
L
-
mixture (hexaneeethyl acetate, 5:1) gave 49 mg (91%) of the title
20
compound as a foam. [
a]
97.3 (c 0.3, chloroform); nmax (film):
D
b
-
L
3020, 2936, 1745, 1606, 1512, 1372, 1235, 1101, 1065, 1027, 849,
b
-L
759 cmꢁ1. 1H NMR (CDCl3)
d: 7.97e7.99 (m, 2H, Ar), 6.91e6.93 (m,
mixture of 61 and 62 (395 mg, 0.54 mmol) was silylated using the
procedure described for 7. Column chromatography of the crude
product (hexaneeethyl acetate, 40:1/5:1; all eluents contained
0.5% Et3N) afforded 63 (219 mg, 48%) and a mixture of 63 and 64
(125 mg, 27%).
2H, Ar), 5.84e5.90 (m, 1H, CH¼), 5.28e5.31 (m, 1H,¼CHH), 5.26 (t,
1H, J3,2¼J3,4¼7.4 Hz, H-30), 5.20e5.23 (m, 2H, H-4,¼CHH), 5.13 (dd,
1H, J2,1 3.6, J2,3 10.1 Hz, H-2), 5.05e5.07 (m, 2H, H-1, H-20), 4.95 (m,
1H, H-40), 4.82 (d, 1H, J1,2 5.1 Hz, H-10), 4.29 (dd, 01H, J3,2 10.2, J3,4
0
3.5 Hz, H-3), 4.24 (dd, 1H, J5,4 4.5, J5,5 12.3 Hz, H-5 ), 4.15e4.20 (m,
Method B. Disaccharide 59 (98 mg, 0.12 mmol) was converted
into 1-propenyl derivative 63 using the procedure described for 8.
Column chromatography of the crude product (hexaneeethyl ace-
tate, 40:1/5:1; all eluents contained 0.5% Et3N) afforded 63
1H, OCHH), 3.98e4.02 (m, 1H, OCHH), 3.86 (s, 3H, OCH3), 3.83 (dd,
0
0
1H, J5,4 1.2, J5,5 12.9 Hz, H-5), 3.65 (dd, 1H, J5,4 2.4, J5,5 12.9 Hz, H-5),
0
0
3.53 (dd, 1H, J5,4 6.4, J5,5 12.3 Hz, H-5 ), 2.13 (s, 3H, CH3), 2.06 (s, 3H,
CH3), 1.95 (s, 3H, CH3), 1.82 (s, 3H, CH3). 13C NMR (CDCl3)
d: 170.3,
(91 mg, 93%).
170.2, 169.9, 169.7, 164.3, 163.7, 133.5, 132.0, 121.6, 117.9, 113.7, 97.3
(C-10), 95.5 (C-1), 70.3 (C-3), 70.0 (C-30), 69.9 (C-20), 69.2 (C-2), 68.7
(C-40), 68.6 (OCH2), 67.4 (C-4), 61.3 (C-50), 60.4 (C-5), 55.4, 20.9,
20.8, 20.6, 20.5. HRMS (ESI) calcd for C29H36NaO15 [MþNa]þ:
647.1952. Found: 647.1946.
20
Data for 63: [
a]
56.2 (c 0.30, chloroform); 1H NMR (CDCl3)
d:
D
8.02e8.03 (m, 2H, Ar), 6.90e6.91 (m, 2H, Ar), 6.12 (dq, 1H, J 1.5,
12.2 Hz, OCH¼), 5.14 (dd, 1H, J2,1 2.4, J2,3 7.1 Hz, H-20), 5.05e5.11 (m,
2H, H-10,¼CH), 4.96 (dd, 1H, J2,1 5.6, J2,3 6.8 Hz, H-2), 4.80 (d, 1H, J1,2
0
5.6 Hz, H-1), 4.08 (dd, 1H, J5,4 3.9, J5,5 11.8 Hz, H-5), 4.03 (dd, 1H, J3,2
7.1, J3,4 2.6 Hz, H-30), 3.93e3.95 (m, 1H, H-40), 3.87 (s, 3H, OCH3),
3.74 (t,1H, J3,2 6.8, J3,4 6.8 Hz, H-3), 3.65e3.68 (m, 1H, H-4), 3.50 (d0d,
5.2.34. 2-O-(4-Methoxybenzoyl)-3,4-di-O-triethylsilyl-
b-L-xylopyr-
anosyl-(1/3)-2-O-acetyl-4-O-triethylsilyl- -arabinopyranose
a,b-L
0
0
0
1H, J5,4 3.0, J5,5 11.5 Hz, H-5 ), 3.42 (dd, 1H, J5,4 6.6, J5,5 11.5 Hz, H-5 ),
(67). Hydrolysis of 1-propenyl glycoside 63 (264 mg, 0.31 mmol)
was performed using the procedure described for 9. Column
chromatography of the crude product (hexaneeethyl acetate, 7:3;
0
3.26 (dd,1H, J5,4 7.5, J5,5 11.8 Hz, H-5), 2.10 (s, 3H, CH3),1.53 (dd,1H, J
1.5, 6.9 Hz, CH3), 0.94 (t, 9H, J 7.9 Hz, CH3), 0.87e0.90 (m, 18H, CH3),
0.49e0.63 (m, 18H, CH2). 13C NMR (CDCl3)
d
: 169.9, 164.9, 163.3,
contained 0.5% Et3N) afforded 67 (210 mg, 84%,
a,b mixture in 1:1
143.4, 131.8, 122.7, 113.4, 104.6, 100.0 (C-1), 96.2 (C-10), 73.6 (C-3),
73.3 (C-2,30), 70.9 (C-4), 70.0 (C-20), 66.7 (C-40), 64.4 (C-5), 64.2 (C-
50), 55.4, 20.9, 12.3, 6.8, 6.7, 4.9, 4.9, 4.7. Anal. Calcd for C41H72O12Si3
(841.28): C, 58.54; H, 8.63. Found: C, 58.46; H, 8.41.
ratio) as foam. 13C NMR (CDCl3)
d
: selected signalsd170.2, 169.4,
165.8,165.1,163.5,163.3,132.0,131.9,122.8,122.4,113.5,113.4,101.3,
101.3, 91.6, 91.2, 75.5, 74.2, 73.5, 73.5, 72.8, 72.7, 72.0, 71.3, 70.7,
70.6, 70.6, 66.3, 65.2, 65.1, 64.2, 64.1, 58.6, 55.4, 55.4, 20.9, 20.9.