69451 weinheim, germany - wiley-vch · 2007. 5. 16. · 4145.78 414 4.80 4148.81 4149.03 4149.79...
TRANSCRIPT
Supporting Information
© Wiley-VCH 2007
69451 Weinheim, Germany
LC-MS analysis of products obtained by glycosylation of 17 with a 9:1 mixture of 8 and 9
C196H200F3N11O85 M calc: 4124.16; 4126.17 (100%)
M found: 4147.11 [M+Na]+
05.0 10.0 15.0 20.0 t [min]
rel. Int. [%]100
4060 4080 4100 4120 4140 4160 4180 4200m/z [amu]
0
0
4119.37
4116.784076.68
4142.244123.25 4147.11
4077.43
4074.864104.614100.20
4081.734119.37
rel. Int. [%]
rel. Int. [%]
4163.29
2322
22
23
RP-HPLC ESI-MS
C194H198F3N11O84 M calc: 4082.15; 4084.16 (100%)
M found: 4105.03 [M+Na]+
3600 3650 3700 3750 3800 3850 3900 3950 4000 4050 4100 4150 4200 4250 4300 4350 4400 44500
100 4147.73
4147.08
4121.004119.92
4118.84
4105.89
4105.13
4078.98
4069.31
4148.81
4149.03
4149.79
4164.87
4165.63
4166.06
4166.93
4167.37
4167.80
4169.11
4171.50
4172.91
4186.51
4144 4146 4148 4150 4152 4154 4156 4158 4160 4162 4164 4166 4168 4170 4172 41740
100
%
4147.73
4147.08
4145.78
4144.80
4148.81
4149.03
4149.79
4164.87
4163.67
4162.81
4150.87
4151.20
4151.524161.834151.74
4152.06
4152.61
4153.04
4153.80
4161.07
4165.63
4166.06
4166.93
4167.37
4167.80
4169.114170.84
4171.50
4172.914173.24
m/z [amu]
rel. Int. [%]C196H200F3N11O85M calc: 4124.16; 4126.17 (100%)
M found: 4147.08 [M+Na]+
22
3750 3800 3850 3900 3950 4000 4050 4100 4150 4200 4250 43000
100 4076.32
4075.89
4074.82
4073.64
4016.724016.084014.80
4017.144018.744019.59
4033.52
4077.17
4078.35
4078.57
4079.42
4079.74
4080.284103.754105.25
4106.43
4138.484136.97 4139.77
rel. Int. [%]
m/z [amu]
23 C194H198F3N11O84 M calc: 4082.15; 4084.16 (100%)
M found: 4105.25 [M+Na]+
4077.17 [M-N +Na]+2
4072 4074 4076 4078 4080 4082 4084 4086 4088 4090 4092 4094 4096 4098 4100 4102 4104 4106 4108 4110 4112 41140
100 4076.32
4075.89
4074.82
4073.64
4077.17
4078.35
4078.57
4079.42
4079.74
4080.284103.75
4103.10
4092.274080.924091.52
4090.34
4093.774102.25
4095.17 4101.174099.03
4104.294105.25
4106.43
4107.18
4108.58
3450 3500 3550 3600 3650 3700 3750 3800 3850 3900 3950 4000 4050 4100 4150 4200 4250 4300 4350 4400 44500
100
%
3977.24
3977.03
3976.71
3976.39
3975.97
3975.75
3975.44
3974.90
3974.48
3593.36
3592.55
3592.15
3535.19
3533.09 3591.14
3594.87
3917.913595.28
3917.49
3914.54
3978.94
4005.05
4006.43
4007.29
4007.61
4008.68
4041.84
4060.41
4099.41
m/z [amu]
rel. Int. [%]
OAcO
OO
NPht
O
AcO
AcOAcO
O
NPht
AcO
AcOAcO
O
AcO
OOAc
O
NPht
BzlO N3O
NPht
OBzl
OBzlO O
O
NHTFAc
AcO
AcOAcO
OHO
O
O
O
NHTFAc
O
AcO
AcOAcO
O
NHTFAc
AcO
AcOAcO
O
O
NHTFAc
AcO
AcOAcO
O
O OMe
24
3974 3976 3978 3980 3982 3984 3986 3988 3990 3992 3994 3996 3998 4000 4002 4004 4006 4008 4010 40120
100 3976.92
3976.60
3975.54
3974.90
3977.35
3977.99
3978.63
3978.94
4000.033979.58
3998.97
3980.11
3980.54
3980.97
3998.013981.50
3997.58
4003.774001.53
4002.59
4005.69
4005.90
4006.43
4006.76
4007.29
4008.574011.77
3950 4000 4050 4100 4150 4200 4250 4300 4350 4400 4450 4500 4550 4600 4650 4700 4750 4800 4850 4900 49500
100
%
4377.734377.39
4376.50
4375.83
4375.50
4374.71
4374.49
4316.804257.414287.93
4378.51
4378.84
4379.29
4380.29
4380.63
4381.08
4403.544405.44
4407.23
4408.354409.70
rel. Int. [%]
m/z [amu]
O
AcO
OO
NPht
O
AcO
AcOAcO
O
NPht
AcO
AcOAcO
O
AcO
O
OAc
O
NPht
BzlO N3O
NPht
OBzl
OBzlO O
O
NHTFAc
AcO
AcOAcO
O
HO
O
O
O
NHTFAc
O
AcO
AcOAcO
O
NHTFAc
AcO
AcOAcO
O
O
NHTFAc
AcO
AcOAcO
O
OH3COMpm
OMpmMpmO
O
4370 4372 4374 4376 4378 4380 4382 4384 4386 4388 4390 4392 4394 4396 4398 4400 4402 4404 4406 4408 4410 4412 44140
1004377.77
4376.83
4375.94
4375.50
4374.71
4374.49
4374.16
4378.06
4378.51
4379.51
4380.52
4381.30
4405.554404.214394.93
4393.254382.64
4392.134390.794383.31
4383.754389.90
4403.654400.294399.06
4398.06
4406.56 4408.02
4411.824409.81
26
O
AcO
OO
NPht
O
AcO
AcOAcO
O
NPht
AcO
AcOAcO
O
AcO
O
OAc
O
NPht
BzlO N3O
NPht
OBzl
OBzlO O
O
NPht
AcO
AcOAcO
O
HO
O
O
O
NPht
O
AcO
AcOAcO
O
NPht
AcO
AcOAcO
O
O
NHTFAc
AcO
AcOAcO
O
O OMe
23
HCO2H
O
AcO
OO
NPht
O
AcO
AcOAcO
O
NPht
AcO
AcOAcO
O
AcO
O
OAc
O
NPht
BzlO N3O
NPht
OBzl
OBzlO O
O
NHTFAc
AcO
AcOAcO
O
HO
O
O
O
NHTFAc
O
AcO
AcOAcO
O
NHTFAc
AcO
AcOAcO
O
O
NHTFAc
AcO
AcOAcO
O
O OMe
24
O
AcO
OO
NPht
O
AcO
AcOAcO
O
NPht
AcO
AcOAcO
O
AcO
O
OAc
O
NPht
BzlO N3O
NPht
OBzl
OBzlO O
O
NHTFAc
AcO
AcOAcO
O
HO
O
O
O
NHTFAc
O
AcO
AcOAcO
O
NHTFAc
AcO
AcOAcO
O
O
NHTFAc
AcO
AcOAcO
O
OH3COMpm
OMpmMpmO
O
26
HCO2H
Compound 24: 14.3 mg (3.59 µmol, 46.6 % yield),
Rf = 0.21 (hexane/acetone, 1:1), [α]D26 = -4.7 (0.9, CH2Cl2),
C176H189F12N11O81 (3982.4),
ESI-MS (100 % acetonitrile): Mcalcd. = 3980.1 Mfound = 4003.8 (M+Na)+,
1H-NMR (500 MHz, [D6]DMSO, 298 K): δ = 9.62 (br, 3H, NH), 9.06 (br, 1H, NH),
7.91-7.64 (m, 16H, NPht), 7.46-6.01 (m, 19H, Ar), 5.64-5.52 (m, 2H, H-35’, H-35),
5.42-5.16 (m, 8H, H-15, H-3B, H-15’, H-12, H-11, H-36’, H-36’’, H-36), 5.12-5.00 (m, 5H, H-45,
H-46, H-4B, H-34, H-16), 4.97 (dd, J3,4 = 9.4 Hz, J4,5 = 8.8 Hz, 1H, H-45’), 4.91-4.76 (m, 5H,
H-46’, H-46’’, H-16’, CH2O, H-23), 4.70 (d, J1,2 = 7.4 Hz, 1H, H-16’’), 4.64-4.49 (m, 5H, H-13,
CH2O, H-14, H-14’, CH2O), 4.44 (d, Jgem = 12.8 Hz, 1H, CH2O), 4.39-4.16 (m, 10H, H-1B,
H-2B, H-6a5’, H-6a5, CH2O, CH2O, H-31, H-6a6’’, H-6a6’, H-6a6), 4.15-3.89 (m, 18H, H-6b5,
H-6aB, H-6b6’, H-6b6’’, H-6a4, H-55’, H-25, H-55, H-6b5’, H-24, H-25’, H-22, H-41, H-32, H-42,
H-6b4, H-33, H-24’), 3.88-3.61 (m, 22H, H-6b6, H-6a1, H-21, H-6a2, H-56’’, H-51, H-5B, H-53,
H-6b1, H-6bB, H-26’, H-56’, H-26’’, H-56, H-43, H-6a4’, H-34’, PhOCH3, H-51, H-54’),
3.55-3.37 (m, 8H, H-26, H-6a3, H-41, H-44’, H-6b2, H-6b4’, H-52, H-6b3), 2.12-1.62 (m, 63H,
21 OAc),
13C-NMR (125 MHz, [D6]DMSO, 298 K): δ = 170.1, 170.1, 170.0, 170.0, 169.9, 169.8,
169.7, 169.6, 169.3 (C=O, OAc), 168.0, 167.4, 167.1 (C=O, NPht), 156.9, 156.6, 156.4,
156.3 (C=O, TFA), 153.4, 151.9 (C-4, C-1; OMp), 138.1, 137.8 (C-1, Ar), 135.0,
134.9 (C-4/5, NPht), 130.6, 130.5, 130.4 (C-1/2, NPht), 128.2, 128.0, 127.8, 127.7, 127.5,
127.3, 126.9, 126.7 (C, Ar), 123.7, 123.5, 123.2 (C-3/6, NPht), 116.9, 116.8, 115.9 (CF3),
115.8 (q, 1JC,F = 287.5 Hz, CF3), 115.3, 114.4 (C-2, C-3, C-5, C-6; OMp), 101.4 (C-1B),
99.7 (C-16’’), 99.5 (C-13), 99.3 (C-16), 98.5 (C-16’), 97.1 (C-14), 97.1 (C-12), 96.1 (C-14’),
95.7 (C-15), 95.3 (C-15’), 84.4 (C-11), 77.6 (C-24), 77.1 (C-31), 76.7 (C-52), 76.2 (C-32),
76.2 (C-42), 76.1 (C-44), 75.9 (C-31), 74.7 (C-51), 74.4 (C-54’), 73.6 (C-24’), 73.6 (CH2O),
73.0 (CH2O), 72.5 (C-44’), 72.2 (C-36’), 72.2 (CH2O), 71.6 (C-3B), 71.6 (C-36’’), 71.6 (C-5B),
71.1 (C-36), 71.1 (C-56’), 71.1 (C-56), 70.7 (C-34’), 70.6 (C-56’’), 70.6 (C-41), 70.6 (C-55),
70.3 (C-55’), 70.1 (C-31), 69.9 (C-35), 69.9 (C-35’), 69.2 (C-4B), 68.8 (C-34), 68.3 (C-45’),
68.3 (C-64’), 68.3 (C-54), 68.1 (C-46), 68.1 (C-46’), 68.1 (C-23), 67.7 (C-46’’), 67.3 (C-45),
66.9 (C-63), 66.4 (C-61), 62.9 (C-6B), 61.9 (C-62), 61.5 (C-65), 61.5 (C-66), 61.5 (C-66’’),
61.5 (C-66’), 61.2 (C-64), 60.7 (C-65’), 56.1 (C-22), 55.1 (PhOCH3), 54.8 (C-26), 54.3 (C-25’),
54.2 (C-41), 54.2 (C-26’), 54.1 (C-25), 54.1 (C-26’’), 53.9 (C-2B), 20.6, 20.5, 20.4, 20.4, 20.3,
20.2, 20.1, 20.0 (CH3, OAc).
Compound 26: 8.4 mg (1.92 µmol, 75 % yield),
Rf = 0.20 (hexane/acetone, 1:1),
[α]D26 = -26.1 (1.1, CH2Cl2),
C176H189F12N11O81 (4382.9),
ESI-MS (100 % acetonitrile): Mcalcd. = 4380.3 Mfound = 4403.5 (M+Na)+,
1H-NMR (500 MHz, [D6]DMSO, 298 K): δ = 9.67-9.35 (m, 3H, NH), 8.62 (br, 1H, NH),
7.91-7.59 (m, 16H, NPht), 7.34-6.66 (m, 27H, Ar), 5.65-5.51 (m, 2H, H-35’, H-35),
5.42-5.32 (m, 3H, H-15, H-3B, H-15’), 5.29-5.20 (m, 3H, H-12, H-36’, H-36’’), 5.18 (d,
J1,2 = 9.5 Hz, 1H, H-11), 5.12-4.92 (m, 7H, H-36, H-45, H-4B, H-46’, H-34, H-16, H-45’),
4.88-4.73 (m, 6H, H-46’’, H-46, CH2O, H-16’, H-1F, H-23), 4.71-4.27 (m, 19H, CH2O, H-16’’,
CH2O, CH2O, H-13, H-14, H-14’, CH2O, CH2O, CH2O, H-1B, CH2O, CH2O, CH2O, CH2O,
H-2B, CH2O, H-6a5’, H-6a5), 4.22-3.87 (m, 22H, H-6a6’’, H-32, H-6a6’, H-31, H-6aB, H-6a4,
H-6b5, H-25, H-55’, H-55, H-6b5’, H-6b6’’, H-24, H-42, H-25’, H-22, H-6b6’, H-24’, H-41, H-33,
H-6a6, H-6b4), 3.87-3.59 (m, 26H, H-21, H-6a1, H-56’, H-56’’, H-43, H-26’, H-6b6, H-6bB, H-5B,
H-53, PhOCH3, H-56, H-26’’, H-34’, H-5F, H-6a4’, H-2F, H-3F), 3.58-3.17 (m, 14H, H-4F, H-26,
H-51, H-6a3, H-54, H-44’, H-54’, H-6b1, H-6a2, H-6b4’, H-52, H-44, H-6b3, H-6b2),
2.06-1.65 (m, 63H, 21 OAc), 0.90 (d, J5,6 = 5.9 Hz, 3H, H-6F),
13C-NMR (125 MHz, [D6]DMSO, 298 K): δ = 170.8, 170.7, 170.6, 170.4, 170.0, 169.7 (C=O,
OAc), 167.1, 166.9, 166.7 (C=O, NPht), 159.4, 159.3 (C-4, Mpm), 156.5, 156.3, 156.2 (C=O,
TFA), 139.0, 138.5 (C-1, Ar), 135.7, 135.6 (C-4/5, NPht), 132.6, 132.0, 131.7, 131.5,
131.4 (C-1, Mpm; C-1/2, NPht), 130.3, 129.6, 128.9, 128.6, 128.5, 128.4, 128.2, 127.9,
127.6 (C-2/6, Mpm; C, Ar), 124.9, 124.4, 124.2, 123.3 (C-3/6, NPht), 116.8, 115.0,
114.6 (CF3), 114.4 (C-3/5, Mpm), 101.0 (C-1Bβ , 1JC-1,H-1 = 163.2 Hz), 99.5 (C-16’’β,1JC-1,H-1 = 163.8 Hz), 99.5 (C-13β , 1JC-1,H-1 = 166.8 Hz), 98.5 (C-16β , 1JC-1,H-1 = 165.0 Hz),
98.5 (C-16’β , 1JC-1,H-1 = 166.8 Hz), 97.1 (C-14α , 1JC-1,H-1 = 178.6 Hz), 96.9 (C-12β,1JC-1,H-1 = 167.2 Hz), 96.5 (C-14’α , 1JC-1,H-1 = 177.4 Hz), 95.6 (C-15β , 1JC-1,H-1 = 166.5 Hz),
95.4 (C-15’β , 1JC-1,H-1 = 167.2 Hz), 93.9 (C-1Fα , 1JC-1,H-1 = 174.0 Hz), 84.2 (C-11β,1JC-1,H-1 = 167.5 Hz), 77.6 (C-3F), 76.9 (C-4F), 76.7 (C-24), 76.7 (C-52), 76.2 (C-43),
75.9 (C-32), 75.9 (C-31), 75.7 (C-42), 75.6 (C-41), 75.6 (C-51), 73.9 (C-2F), 73.6 (CH2O),
73.6 (C-24’), 73.6 (C-44’), 73.0 (CH2O), 72.6 (C-54’), 71.8 (CH2O), 71.8 (C-36’), 71.4 (C-3B),
71.4 (C-56’’), 71.2 (C-36’’), 71.2 (C-36), 70.9 (CH2O), 70.6 (C-56), 70.6 (CH2O), 70.5 (C-55),
70.5 (C-56’), 70.5 (C-5B), 70.5 (C-53), 70.5 (CH2O), 70.5 (C-44), 70.0 (C-55’), 69.8 (C-35),
69.7 (C-34), 69.5 (C-35’), 69.5 (C-54), 69.1 (C-4B), 68.1 (C-34’), 68.1 (C-64’), 68.1 (C-33),
68.9 (C-46’), 68.9 (C-45’), 68.9 (C-46’’), 68.9 (C-46), 68.9 (C-23), 67.3 (C-45), 66.9 (C-63),
65.4 (C-5F), 63.9 (C-62), 62.6 (C-6B), 61.7 (C-61), 61.2 (C-65), 61.2 (C-66’’), 61.2 (C-66’),
61.2 (C-64), 61.2 (C-66), 60.6 (C-65’), 55.6 (C-22), 54.5 (C-26’), 54.6 (C-26), 54.6 (PhOCH3),
54.3 (C-25’), 54.2 (C-21), 54.0 (C-25), 53.8 (C-2B), 53.8 (C-26’’), 21.3, 21.2, 20.9, 20.8 (CH3,
OAc), 16.9 (C-6F).
CH-coupling constants determined by coupled HSQC experiment:
G. Bodenhausen, D. J. Ruben, Chem. Phys. Lett. 1980, 69, 185-188.