4144
S. Vogel et al. / Tetrahedron 57 22001) 4139±4146
1
80%).- H NMR 2400MHz, D2O): characteristic signals at
d1.13 2s, CH3-4F), 1.29 2d, CH3-6C), 1.94, 2.00 2s,
2negative mode): m/z1324.49514 21324.47134) [M-H]-,
661.73478 2661.73203) [M-2H]2-.
NHCOCH3 , s, NHCOCH3 ), 4.13 2s, H-4B, H-5B), 4.35
2s, H-5F), 4.49 2d, H-1D), 4.92 2d, H-3F), 5.03 2d,
CHCHtrans-5I), 5.03 2d, CHCHcis-5I), 5.69 2q, H-1F),
E
C
4.1.10. /R)-3-/{b-d-Galactopyranuronamidosyl-/1!4)-
2-acetamido-2,6-dideoxy-b-d-glucopyranosyl-/1!4)-[b-
d-glucopyranosyl-/1!6)]-2-acetamido-2-deoxy-b-d-
glucopyranosyl-/1!2)-3-O-carbamoyl-4-C-methyl-a-d-
glucopyranuronamidosyloxy}hydroxyphosphoryloxy)-
2-//2J,3J)-2-hydroxy-3-phenyl-4-pentenyl-oxy)-pro-
pionic acid /9b). 9b was prepared from 4 260.3 mg,
50 mmol) and cinnamyl chloride 238.7 mg, 200 mmol) as
described for 9f. Yield: 63mg, 95%.- 1H NMR 2H,H
COSY, D2O, 400MHz): characteristic signals at d1.19
5.70±5.80 2m, CHCH2-4I), J4-5-cis9.1 Hz, J4-5-trans
15.6 Hz.-13C NMR 2100 MHz, D2O): d14.25 2CH3-4F),
E
C
16.21 2CH3-6C), 21.85 2NHCOCH3 , NHCOCH3 ), 36.49
2C-3I), 54.71, 55.06 2C-2E, C-2C), 60.37 2C-6D), 68.41
2C-3H), 69.28, 70.15, 70.69, 71.57, 71.76, 72.05, 72.63,
73.08, 73.42, 73.86, 74.51, 75.36, 75.57 2C-5C, C-4D,
C-4B, C-2B, C-3B, C-3C, C-5F, C-6E, C-5B, C-3E, C-2F,
C-4F, C-5E, C-2D, C-3F, C-5D, C-3D, C-1I, C-2I), 79.34
2C-4E), 79.90 2C-2H), 82.60 2C-4C), 93.96 2C-1F), 100.84,
101.80, 102.19, 102.82 2C-1C, C-1E, C-1B, C-1D), 117.35
2s, CH3-4F), 1.32 2d, CH3-6C), 1.99, 2.04 2s, NHCOCH3 ,
E
C
s, NHCOCH3 ), 3.27 2dd, H-2D), 4.17 2s, H-4B, H-5B), 4.40
2C-5I), 134.00 2C-4I), 157.74 2OCONH2 ), 172.33, 172.80
2s, H-5F), 4.46 2d, H-1D), 4.98 2d, H-3F), 5.09 2d, CHCHcis-
11I), 5.15 2d, CHCHtrans-11I), 5.75 2m, H-1F), 6.00±6.12
F
B
F
E
C
2CONH2 , CONH2 ), 174.20 2NHCOCH3 , NHCOCH3 ).-
31P NMR 281 MHz, D2O): d-1.53.- C44H72N5O33P
21230.05, 1229.38) g/mol, ESI MS 2negative mode):
m/z1250.35304 21250.35927) [M-2H1Na]-, 1228.37638
21228.37744) [M-H]-, 613.68415 2613.68508) [M-2H]2-,
FAB MS: m/z1252.3 [M1Na]1, 1230.2 [M1H]1.
2m, CHCH2-10I), 7.26±7.39 2m, H-5I±H-9I), J5C-6C
5.3 Hz, J2D-3D8.5 Hz, J1D-2D7.8 Hz, J2F-3F10.3 Hz,
NMR
J10I-11I-cis10.2 Hz,
J10I-11I-trans17.3 Hz.-
13C
2100 MHz, D2O): d15.03 2CH3-4F), 16.90 2CH3-6C),
E
C
22.56, 22.65 2NHCOCH3 , NHCOCH3 ), 53.50 2C-3I),
55.24, 55.76 2C-2E, C-2C), 61.05 2C-6D), 66.97 2C-3H),
68.90, 69.15, 69.94, 70.85, 71.37, 72.18, 72.46, 72.59,
72.73, 72.84, 73.17, 73.28, 73.35, 73.76, 74.50, 75.13,
76.07, 76.27, 76.37, 76.47 2C-5C, C-4D, C-4B, C-2B, C-3B,
C-3C, C-5F, C-6E, C-5B, C-3E, C-2F, C-4F, C-5E, C-2D, C-3F,
C-5D, C-3D, C-1I, C-2I), 79.88 2C-4E), 80.21 2C-2H), 83.25
2C-4C), 94.80 2C-1F), 101.45, 102.41, 102.83, 103.42 2C-1C,
C-1E, C-1B, C-1D), 117.28 2C-11I), 127.29 2C-7I), 128.69,
129.22 2C-5I, C-9I, C-6I, C-8I), 138.64 2C-10I), 141.45
4.1.9. /R)-3-/{b-d-Galactopyranuronamidosyl-/1!4)-2-
acetamido-2,6-dideoxy-b-d-glucopyranosyl-/1!4)-[b-d-
glucopyranosyl-/1!6)]-2-acetamido-2-deoxy-b-d-gluco-
pyranosyl-/1!2)-3-O-carbamoyl-4-C-methyl-a-d-gluco-
pyranuronamidosyloxy}hydroxyphosphoryloxy)-2-
//2J,3J)-2-hydroxy-3,7-dimethyl-3-vinyl-6-octeny-
loxy)-propionic acid /9f). To a solution of 4 260 mg,
50 mmol) in a mixture of water 2400 ml) and methanol
21.6 ml) geranyl bromide 243.8 mg, 200 mmol) and indium
223.2 mg, 200 mmol) were added. The mixture was soni-
cated for 60 min and then stirred at 208C for 24 h. The
crude reaction mixture was directly applied to a Sepha-
dexe LH-20 column 2H2O-CH3OH 1:4). Product fractions
were concentrated and freeze-dried. The crude product was
puri®ed by FC 2ethyl acetate-2-propanol-H2O 6:4:2) and
subsequently by gel ®ltration 2Sephadex LH-20w, H2O-
CH3OH 1:4). The combined fractions were concentrated
and freeze-dried to give 9f 220.3 mg, 30%).- 1H NMR
2H,H COSY, 400MHz, D2O): characteristic signals at
d0.96 2s, CH3-10I), 1.18 2s, CH3-4F), 1.33 2d, CH3-6C),
1.35±1.40 2m, CH2-4I), 1.56, 1.64 2s, CH3-8I, CH3-9I),
F
B
2C-4I), 158.37 2OCONH2 ), 172.92±174.82 2CONH2 ,
CONH2 , NHCOCH3 , NHCOCH3 ).- 31P NMR 281 MHz,
D2O) d-1.43.- C50H76N5O33P 21306.15, 1305.42), ESI MS
2negative mode): m/z1304.40652 21304.40874) [M-H]-,
651.70161 2651.70031) [M-2H]2-, FAB MS: m/z1306.2
[M1H]1.
F
E
C
4.1.11. /R)-3-/{b-d-Galactopyranuronamidosyl-/1!4)-
2-acetamido-2,6-dideoxy-b-d-glucopyranosyl-/1!4)-[b-
d-glucopyranosyl-/1!6)]-2-acetamido-2-deoxy-b-d-
glucopyranosyl-/1!2)-3-O-carbamoyl-4-C-methyl-a-d-
glucopyranuronamidosyloxy}hydroxyphosphoryloxy)-
2-//2J,3J,6E)-2-hydroxy-3,7,11-trimethyl-3-vinyl-6,10-
dodecadienyloxy)-propionic acid /9g). 9g was prepared
from 4 260 mg, 50 mmol) and 2E,E)-farnesyl bromide
257.6 mg, 200 mmol) as described for 9f. Yield: 9.8 mg,
E
1.85±1.93 2m, CH2-5I), 1.99, 2.05 2s, NHCOCH3 , s,
NHCOCH3 ), 3.26 2dd, H-2D), 4.18 2s, H-4B, H-5B), 4.41
C
2s, H-5F), 4.47 2d, H-1D), 4.98 2d, H-3F), 5.03 2m,
CHCHtrans-12I), 5.12 2m, CHCHcis-12I), 5.05 2m,
CHC2CH3)2-6I), 5.75 2m, H-1F), 5.75±5.85 2m,
CHCH2-11I), J5C-6C4.9 Hz, J2D-3D8.3 Hz, J1D-2D8.8
Hz, J2F-3F10.8 Hz, J11I-12I-cis11.3 Hz, J11I-12I-trans18.1 Hz.-
13C NMR 2100 MHz, D2O): d15.19 2CH3-4F), 16.21, 16.70,
1
14%.- H NMR 2H,H COSY, 400MHz, D2O, assigments
were made according to the geranyl derivative): character-
istic signals at d0.95 2s, CH3-15I), 1.11, 1.12 23H, ?), 1.17
2s, CH3-4F), 1.33 2d, CH3-6C), 1.36±1.40 2m, CH2-4I), 1.53
2CH3-14I), 1.57, 1.64 2s, CH3-12I, s, CH3-13I), 1.85±1.92
2m, CH2-5I), 1.95±2.00 2m, CH2-8I), 2.02±2.10 2m, CH2-
16.79 2CH3-6C, C-9I, C-5I), 22.27±22.43 2NHCOCH3 ,
E
C
E
C
NHCOCH3 , C-8I), 24.83 2C-10I), 37.62 2C-4I), 42.94 2C-
9I), 1.98, 2.05 2s, NHCOCH3 , s, NHCOCH3 ), 3.25 2dd,
H-2D), 4.17 2s, H-4B, H-5B), 4.40 2s, H-5F), 4.46 2d, H-1D),
4.96 2d, H-3F), 5.03 2d, CHCHtrans-17I), 5.12 2d, CH
CHcis-17I), 5.13±5.20 2m, CHC2CH3)2-10I, CHC2CH3)-
CH2-6I), 5.75 2m, H-1F), 5.76±5.81 2m, CHCH2-11I),
3I), 55.38±55.60 2C-2E, C-2C), 61.43 2C-6D), 69.31±77.24
2C-5C, C-4D, C-4B, C-2B, C-3B, C-3C, C-5F, C-6E, C-5B, C-
3E, C-2F, C-4F, C-5E, C-2D, C-3F, C-5D, C-3D, C-1I, C-2I, C-
2H), 80.95 2C-4E), 83.51 2C-4C), 94.68 2C-1F), 101.78,
102.42, 103.16, 103.43 2C-1C, C-1E, C-1B, C-1D), 113.49
2C-12I), 124.86 2C-6I), 131.22 2C-7I), 143.48 2C-11I),
J5C-6C5.8 Hz, J2D-3D7.8 Hz, J1D-2D7.8 Hz, J2F-3F
10.5 Hz, J16I-17I-cis11.5 Hz, J16I-17I-trans17.8 Hz.- 13C NMR
F
B
F
158.07 2OCONH2 ), 172.89±173.54 2CONH2 , CONH2 ,
NHCOCH3 , NHCOCH3 ).- 31P NMR 281 MHz, D2O):
d-2.09.- C51H84N5O33P 21326.23, 1325.47), ESI MS
2100 MHz, D2O): d16.01, 16.13 2CH3-14I, CH3-4F), 17.77
2CH3-6C, C-13I), 23.13 2C-5I), 23.37±23.43 2NHCOCH3 ,
E
C
E
NHCOCH3 ), 25.86 2CH3-12I, CH3-15I), 27.34 2C-9I), 38.53
C