Glycosyl Azides – An Alternative Way to Disaccharides
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(C-3’), 74.2 (C-3), 75.2 (C-5), 75.5 (C-5’), 95.4 (C-1), 103.7
(C-1’). The spectroscopic data of 13 were in accord with the
literature values.[25]
1.207 mmol) were dissolved in citrate/phosphate buffer
(2.4 mL, 0.05M, pH 5.0). b-Gluctosidase from Penicillium
chrysogenum CCF 1269 (12 U) was added and the reaction
mixture was shaken (850 rpm) at 358C and monitored by
TLC (2-propanol:H2O:aqueous NH4OH, 7:2:1). The reac-
tion was stopped after 5 h by heating (1008C, 2 min) and
centrifuged (13,500 rpm, 10 min). Purification by gel chro-
matography (Bio-Gelꢁ P-2; mobile phase H2O, flow rate
14.7 mLhꢁ1, ambient temperature) afforded compound 16 as
a white solid; yield: 17 mg (0.044 mmol; 28% related to
consumed donor 3; donor 3 was partially recovered: 19 mg).
For NMR characterization, compound 16 was peracetylated
(Ac2O/dry py, DMAP, 24 h) and purified by silica gel chro-
matography (CH2Cl2/MeOH, 20:1) to afford peracetate 16a.
According to NMR data, 16a was a mixture of two anomers
(a/b=1.22).
b-d-Galactopyranosyl-(1!6)-2-acetamido-2-deoxy-d-
mannopyranose (15)
b-d-Galactopyranosyl azide (2; 51 mg, 0.249 mmol) and 2-
acetamido-2-deoxy-d-mannopyranose
(14;
266 mg,
1.202 mmol) were dissolved in phosphate buffer (1.8 mL,
0.05M, pH 7.3). b-Galactosidase from E. coli (26 U) was
added and the reaction mixture was shaken (850 rpm) at
358C and monitored by TLC (2-propanol: H2O:aqueous
NH4OH, 7:2:1). The reaction was stopped after 4.5 h by
heating (1008C, 2 min) and centrifuged (13,500 rpm,
10 min). Purification by gel chromatography (Bio-Gelꢁ P-2;
mobile phase H2O, flow rate 13.8 mLhꢁ1, ambient tempera-
ture) afforded compound 15 as a white solid; yield: 6.7 mg
(0.017 mmol; 14% related to consumed donor 2; donor 2
was partially recovered: 26 mg). [a]2D3: +10.0 (c 0.12 in
water). According to NMR data, 15 was a mixture of two
anomers (a/b=1.22).
1
a-Anomer of 16a: H NMR (CDCl3): d=1.934 (s, 3H, 2-
NAc), 1.999 (s, 3H, Ac), 2.020 (s, 3H, Ac), 2.034 (s, 3H,
Ac), 2.047 (s, 3H, Ac), 2.056 (s, 3H, Ac), 2.089 (s, 3H, Ac),
2.188 (s, 3H, Ac), 3.508 (dd, J6d,6u =10.9 Hz, J5,6u =6.6 Hz,
1H, H-6u), 3.679 (ddd, J4’,5’ =9.9 Hz, J5’,6’d =4.6 Hz, J5’,6’u
2.4 Hz, 1H, H-5’), 3.895 (dd, J5,6d =10.9 Hz, J5,6d =2.0 Hz,
1H, H-6d), 3.945 (ddd, J4,5 =10.5 Hz, J5,6u =6.6 Hz, J5,6d
=
a-Anomer of 15: 1H NMR (D2O; 1JC-1,H-1 =176 Hz): d=
1.828 (s, 3H, Ac), 3.349 (dd, J1’,2’ =7.8 Hz, J2’,3’ =9.9 Hz, 1H,
H-2’), 3.445 (dd, J2’,3’ =9.9 Hz, J3’,4’ =3.4 Hz, 1H, H-3’), 3.483
(ddd, J4ꢃ,5ꢃ =1.0 Hz, J5ꢃ,6’u =4.2 Hz, J5ꢃ,6’d =7.9 Hz, 1H, H-5’),
3.489 (dd, J3,4 =9.9 Hz, J4,5 =10.0 Hz, 1H, H-4), 3.528 (dd,
=
2.0 Hz, 1H, H-5), 4.113 (dd, J6’d,6’u =12.3 Hz, J5’,6’u =2.4 Hz,
1H, H-6’u), 4.283 (dd, J6’d,6’u =12.3 Hz, J5’,6’d =4.6 Hz, 1H, H-
6’d), 4.426 (ddd, J2,2-NH =11.1 Hz, J2,3 =8.9 Hz, J1,2 =3.7 Hz,
1H, H-2), 4.522 (d, J1’,2’ =8.0 Hz, 1H, H-1’), 4.954 (dd, J2’,3’
9.6 Hz, J1’,2’ =8.0 Hz, 1H, H-2’), 5.013 (dd, J4,5 =10.5 Hz,
3,4 =9.3 Hz, 1H, H-4), 5.063 (dd, J4’,5’ =9.9 Hz, J3’,4’ =9.5 Hz,
=
J
5’,6’u =4.2 Hz, J6’u,6’d =11.6 Hz, 1H, H-6’u), 3.585 (dd, J5’,6’d
7.9 Hz, J6’u,6’d =11.6 Hz, 1H, H-6’d), 3.707 (dd, J3’,4’ =3.4 Hz,
4’,5’ =1.0 Hz, 1H, H-4’), 3.727 (dd, J5,6u =4.8 Hz, J6u,6d
11.3 Hz, 1H, H-6u), 3.794 (ddd, J4,5 =10.0 Hz, J5,6u =4.8 Hz,
5,6d =2.0 Hz, 1H, H-5), 3.834 (dd, J2,3 =4.7 Hz, J3,4 =9.9 Hz,
=
J
1H, H-4’), 5.197 (dd, J2’,3’ =9.6 Hz, J3’,4’ =9.5, 1H, H-3’),
5.212 (dd, J2,3 =11.1 Hz, J3,4 =9.3 Hz, 1H, H-3), 5.546 (d,
J
=
J
2,2-NH =8.9 Hz, 1H, 2-NH), 6.147 (d, J1,2 =3.7 Hz, 1H, H-1);
J
13C NMR (CDCl3, HMQC readouts): d=23.9–24.5 (7ꢂAc),
26.7 (2-NAc), 54.7 (C-2), 65.4 (C-6’), 72.0 (C-4, C-4’), 71.8
(C-6), 74.4 (C-3), 74.6 (C-5, C-2’), 75.6 (C-5’), 76.3 (C-3’),
94.0 (C-1), 104.3 (C-1’).
1H, H-3), 3.946 (dd, J5,6d =2.0 Hz, J6u,6d =11.3 Hz, 1H, H-
6d), 4.101 (dd, J1,2 =1.6 Hz, J2,3 =4.7 Hz, 1H, H-2), 4.235 (d,
J
1’,2’ =7.8 Hz, 1H, H-1’), 4.896 (d, J1,2 =1.6 Hz, 1H, H-1);
13C NMR (D2O, HMQC and HMBC readouts): d=22.0
(Ac), 53.4 (C-2), 61.1 (C-6’), 66.7 (C-4), 68.7 (C-3, C-6), 68.8
(C-4’), 70.8 (C-2’), 71.0 (C-5), 72.8 (C-3’), 75.4 (C-5’), 93.2
(C-1), 103.3 (C-1ꢃ), 174.8 (CO).
1
b-Anomer of 16a: H NMR (CDCl3): d=1.924 (3H, s, 2-
NAc), 2.002 (s, 3H, Ac), 2.020 (s, 3H, Ac), 2.044 (s, 3H,
Ac), 2.056 (s, 6H, 2ꢂAc), 2.096 (s, 3H, Ac), 2.113 (s, 3H,
Ac), 3.592 (dd, J6d,6u =11.2 Hz, J5,6u =6.1 Hz, 1H, H-6u),
3.672 (ddd, J4’,5’ =9.6 Hz, J5’,6’d =4.6 Hz, J5’,6’u =2.2 Hz, 1H, H-
5’), 3.749 (dd, J4,5 =9.6 Hz, J5,6u =6.1 Hz, J5,6d =2.4 Hz; 1H,
H-5), 3.906 (dd, J6d,6u =11.2 Hz, J5,6d =2.4 Hz, 1H, H-6d),
4.128 (dd, J6’d,6’u =12.4 Hz, J5,6’u =2.2 Hz, 1H, H-6’u), 4.232
(ddd, J2,3 =10.3 Hz, J2,2-NH =9.6 Hz, J1,2 =8.8 Hz, 1H, H-2),
4.264 (dd, J6’d,6’u =12.4 Hz, J5’,6’d =4.6 Hz, 1H, H-6’d), 4.551
b-Anomer of 15: 1H NMR (D2O; 1JC-1,H-1 =161 Hz): d=
1.867 (s, 3H, Ac), 3.34[a] (m, 1H, H-5), 3.356 (dd, J1’,2’
=
7.8 Hz, J2’,3’ =9.9 Hz, 1H, H-2’), 3.36[a] (m, 1H, H-4), 3.445
(dd, J2’,3’ =9.9 Hz, J3’,4’ =3.4 Hz, 1H, H-3’), 3.486 (ddd, J4’,5’
1.0 Hz, J5’,6u’ =4.2 Hz, J5’,6d’ =7.9 Hz, 1H, H-5’), 3.530 (dd,
5’,6u’ =4.2 Hz, J6u’,6d’ =11.6 Hz, 1H, H-6u’), 3.585 (dd, J5’,6d’
7.9 Hz, J6u’,6d’ =11.6 Hz, 1H, H-6d’), 3.610 (dd, J2,3 =4.5 Hz,
3,4 =9.7 Hz, 1H, H-3), 3.692 (dd, 5,6u =4.7 Hz, J6u,6d =
=
J
=
(d, J1’,2’ =8.0 Hz, 1H, H-1’), 4.970 (dd, J4,5 =9.6 Hz, J3,4
=
J
J
9.6 Hz, 1H, H-4), 4.976 (dd, J2’,3’ =9.5 Hz, J1’,2’ =8.0 Hz, 1H,
H-2’),5.063 (dd, J4’,5’ =9.6 Hz, J3’,4’ =9.6 Hz, 1H, H-4’), 5.101
11.4 Hz, 1H, H-6u), 3.707 (dd, J3’,4’ =3.4 Hz, J4’,5’ =1.0 Hz,
1H, H-4’), 3.999 (dd, J5,6d =1.5 Hz, J6u,6d =11.4 Hz, 1H, H-
6d), 4.235 (dd, J1,2 =1.7 Hz, J2,3 =4.5 Hz, 1H, H-2), 4.243 (d,
(dd, J2,3 =10.3 Hz, J3,4 =9.6 Hz, 1H, H-3), 5.190 (dd, J3’,4’
=
9.6 Hz, J2’,3’ =9.5 Hz, 1H, H-3’), 5.517 (d, JH,2-NH =9.6 Hz,
1H, 2-NH), 5.664 (d, J1,2 =8.8, 1H, H-1); 13C NMR (CDCl3,
HMQC readouts): d=23.9–24.5 (7ꢂAc), 26.7 (2-NAc), 56.8
(C-2), 65.5 (C-6ꢃ), 71.6 (C-6), 72.0 (C-4, C-4’), 74.6 (C-2ꢃ),
75.6 (C-5’), 76.3 (C-3, C-3’), 77.8 (C-5), 96.2 (C-1), 104.4 (C-
1’). The spectroscopic data of 16a were in accord with the
structure.[26]
J
1’,2’ =7.8 Hz, 1H, H-1’), 4.812 (d, J1,2 =1.7 Hz, 1H, H-1);
13C NMR (D2O, HMQC and HMBC readouts): d=22.1
(Ac), 54.2 (C-2), 61.1 (C-6’), 66.6 (C-4), 68.6 (C-6), 68.8 (C-
4’), 70.8 (C-2’), 72.0 (C-3), 72.8 (C-3’), 75.4 (C-5, C-5’), 93.1
(C-1), 103.3 (C-1’), 175.7 (CO),[a] Readout from HMQC;
MS (MALDI-TOF): m/z=406.2 [M+Na]+.
b-d-Glucopyranosyl-(1!6)-2-acetamido-2-deoxy-d-
glucopyranose (16)
b-d-Glucopyranosyl azide (3; 51 mg, 0.249 mmol) and 2-
acetamido-2-deoxy-d-glucopyranose
(12;
267 mg,
Adv. Synth. Catal. 2007, 349, 1514 – 1520
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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