ChemBioChem
10.1002/cbic.201800656
FULL PAPER
J = 9.5 Hz, 1H, H-3ʹ). 13C NMR (125 MHz, D
O): δ 93.3 (C-1ʹ, 1JHʹCʹ = 170.8
and position could be identified from the correlation signals in the COSY
and HSQC spectra), 4.01 (bs, J = 6.6 Hz, 1H), 3.91 – 3.89 (m, 3H including
H-2), 3.82 – 3.76 (m, 2H), 3.74 – 3.69 (m, 2H), 3.64 (dd, J = 10.8, 8.4 Hz,
1H, H-2), 3.61 – 3.60 (bm, 1H), 3.64 (t, J =10.8 Hz, H-3), 3.28 (t, J = 10.2
2
Hz), 92.2 (C-1, 1JHCʹ = 171.9 Hz), 72.4, 72.3, 71.9, 70.9 (C-2ʹ), 69.6 (C-3ʹ),
6
C H
12
7.6 (C-2), 65.8 (C-4), 60.48, 59.80, 54.8 (C-3). HRMS (ESI): calcd for
23NNaO10+, 364.1214; found: 364.1218 [M + Na]+.
-
13
Hz, 1H, H-3), 1.94 (s, 6H, CH
3
CO
2
2
2). C NMR (151 MHz, D O): δ 181.0
(CH
3
CO -
2
2), (102.73 (C-1), 99.1 (C-1), 76.9, 72. 6, 69.6, 68.0, 65.7,
OH, 2/1); [훼]2 +173.0º (c 0.3,
0
For 4-trehalosamine 3, R
f
0.18 (iPrOH/NH
O);[1d] 1H NMR (500 MHz, CD
OH), (Lit.: [훼]D +179.0º c 0.5 in H
δ 5.13 (d, J = 4.0 Hz, 1H, H-1), 5.04 (d, J = 4.0 Hz, 1Hʹ), 4.08 (dt, J = 10.5,
.0 Hz, 1H, H-5), 3.97 (t, J = 10 Hz, 1H, H-3), 3.81-3.70 (m, 6H), 3.67 (dd,
4
D
-
20
59.9, 59.8 (C-3), 57.5 (C-3), 55.0, 23.1 (CH
3
CO
2
2). HRMS (ESI): calcd
CH
3
2
3
OD):
+
+
for C12H N O
25 2 9
, 341.1560; found: 341.1564 [M + H] .
4
J = 10.0, 4.0 Hz, 1H, H-2), 3.59 (dd, J = 10.0, 4.0 Hz, 1H, H-2ʹ), 3.38 (dd,
J = 9.0 Hz, 1H, H-3ʹ), 3.41 (t, J = 10.3 Hz, 2H, H-4ʹ), 3.23 (d, J = 10.5 Hz,
For neotrehalosyl-4,6-diamine 9, R
f
0.2 (iPrOH/NH
OH, 2/1); [훼]20 +15.4
4
D
1
3
(c 0.13, CH OH); H NMR (500 MHz, D O): δ 5.14 (d, J = 4.0 Hz, 1H, H-
2
1
7
5
H, H-4). 13C NMR (101 MHz, CD
2.2, 70.9 (C-2), 70.8 (C-2ʹ), 69.5 (C-4ʹ), 68.5 (C-3), 68.4 (C-5), 60.4, 60.3,
3
OD): δ 93.5 (C-1'), 93.4 (C-1), 72.4,
1), 4.57 (d, J = 8.0 Hz, 1H, H-1), 3.77 – 3.74 (m, 1H, H-5), 3.72 – 3.67 (m,
2H, H-6), 3.64 (dt, J = 10.0, 2.5 Hz, 1H, H-3), 3.52 (dd, J = 3.5, 10.0 Hz,
1H, H-2), 3.49 – 3.41 (m, 2H including H-3 and H-5), 3.39 (t, J = 8.0 Hz,
1H, H-2), 3.37 (t, J = 8.0 Hz, 1H, H-4), 2.85 (h, J = 12.5, 9.0, 3.5 Hz, 1H,
H-6a), 2.68 – 2.60 (m, 1H, H-6b), 2.57 (t, J = 10.0 Hz, 1H, H-4). 13C NMR
+
2.5 (C-4). HRMS (ESI): calcd for C12
H23NNaO10 requires 364.1214;
+
found: m/z 364.1220 [M + Na] .
(125 MHz, D
Hz), 73.5, 73.4, 72.7, 72.6, 71.3, 71.1, 69.1, 60.2 (C-4), 57.2 (C-6). HRMS
ESI): calcd for C12
+, 341.1555; found: 341.1589 [M + H]+.
2
O): δ 102.7 (C-1, 1JCH = 156 Hz), 100.4 (C-1, 1JCH = 169.1
OH, 2/1); [훼]20 +142.0 (c 0.35,
O): δ 5.16 (d, J = 4.0 Hz, 1H, H-1ʹ), 5.12
For 6-trehalosamine 4, R
OH); 1H NMR (500 MHz, D
CH
f
0.16 (iPrOH/NH
4
D
3
2
(
25 2 9
H N O
(d, J = 3.5 Hz, 1H, H-1), 3.92 (td, J = 3.0, 9.5 Hz, 1H, H-5), 3.81 – 3.75 (m,
4
H), 3.69 (dd, J = 12.0, 4.0 Hz, 1H, H-6bʹ), 3.61 (dd, J = 3.5, 10.0 Hz, 1H,
H-2ʹ), 3.58 (dd, J = 4.0, 10.0 Hz, 1H, H-2), 3.40 – 3.35 (two signals (dd and
t) overlapped, 2H, H-6a and H-4ʹ), 3.30 (t, J = 9.5 Hz, 1H, H-4), 3.08 (dd,
For neotrehalosyl 2,4',6'-diamine 10, R
f
0.25 (iPrOH/NH
O): δ 5.09 (d, J = 8.5 Hz, 1H,
OH, 2:1); [훼]20
4
D
16.7 (c 0.6, H
2
O); 1H NMR (500 MHz, D
2
J = 9.0, 13,5 Hz, 1H, H-6b). 13C NMR (125 MHz, D
O): δ 93.3 (C-1), 93.2
C-1ʹ), 72.3, 72.0, 71.8, 71.2 (C-4), 70.8 (C-2), 70.5 (C-2ʹ), 69.3 (C-4ʹ), 67.9
C-5), 60.2 (C-6ʹ), 40.3 (C-6). HRMS (ESI): calcd for C12
64.1214; found: 364.1212 [M + Na]+
H-1), 4.89 (d, J = 8.5 Hz, 1H, H-1), 4.01 (td, J = 2.5, 9.5 Hz, 1H, H-5), 3.87
(dd, J = 2.0, 12.5 Hz, 1H, H-6), 3.71 (dd, J = 5.5, 12.5 Hz, 1H, H-6), 3.67
(q, J = 9.5 Hz, 2H, including H-3 and H-3), 3.54 – 3.42 (m, 4H, including
H-2, H-4, H-5and H-6), 3.28 – 3.17 (m, 2H, including H-4 and H-6), 3.12
2
(
(
3
H
23NNaO10+,
1
3
1
(
dd, J = 9.0, 11.0 Hz, 1H, H-2). C NMR (125 MHz, D
2
O): δ 98.3 (C-1, JCH
1
OH, 2/1); [훼]20 +175.0 (c
4
D
= 166.1 Hz), 95.3 (C-1, J
CH = 167.0 Hz), 76.4 (C-2), 72.2, 71.7, 71.5, 69.4,
For trehalosyl 2,3-diamine 5, R
f
0.23 (iPrOH/NH
OH); H NMR (500 MHz, D O): δ 5.43 (d, J = 4.0 Hz, 1H, H-1),
.25 (d, J = 3.5 Hz, 1H, H-1), 3.96 (dd, J = 9.0, 10.5 Hz, 1H, H-3), 3.91
1
69.0, 60.2 (C-6), 55.0 (C-2), 52.9 (C-4), 39.8(C-6). HRMS (ESI): calcd for
0
5
.8, CH
3
2
+
+
C H N O , 341.1714; found: 340.1708 [M + H] .
12 26 3 8
(dd, J = 4.0, 11.0 Hz, 1H, H-2), 3.86 – 3.78 (m, 3H), 3.73 (dd, J = 5.0, 12.5
Hz, 2H), 3.69 – 3.65 (m, 2H), 3.54 (d, J = 10.5 Hz, 1H, H-3), 3.50 (t, J =
1
3
9
D
6
C
.5 Hz, 1H, H-4), 3.43 (dd, J = 3.5, 11.0 Hz, 1H, H-2). C NMR (125 MHz,
O): δ 92.4 (C-1), 91.0 (C-1), 72.74, 72.70, 69.5 (C-3), 69.3 (C-4), 67.2,
5.7, 60.2, 60.0, 54.5 (C-3), 53.5 (C-2). HRMS (ESI): calcd for
Acknowledgements
2
+
+
Thanks are given to the Ministry of Science and Technology
Department, Taiwan (MOST 107-2627-M-009-002)..
12 9
H24NNaO , 363.1374; found: 363.1366 [M + Na] .
For trehalosyl 3,6,6-triamine 6, R
f
0.18 (iPrOH:NH
OH = 2:1); [훼]20
4
D
+
1
3
165.0 (c 0.7, CH
3
OH); 1H NMR (500 MHz, D
2
O): δ 5.24 (d, J = 4.0 Hz,
Keywords: aminoglycosides • 1,1-disaccharide • glycosylation •
Pico protecting group •trimethylsilyl glycoside acceptor
H, H-1), 5.21 (d, J = 4.0 Hz, 1H, H-1), 4.04 (td, J = 2.5, 9.0 Hz, 1H, H-5),
.98 (ddd, J = 3.0, 8.5, 10.5 Hz, 1H, H-5), 3.93 (dd, J = 3.5, 10.5 Hz, 1H,
H-2), 3.80 (t, J = 9.5 Hz, 1H, H-3), 3.66 (dd, J = 4.0, 10.0 Hz, 1H, H-2),
.59 (t, J = 10.0 Hz, 1H, H-4), 3.55 (t, J = 10.5 Hz, 1H, H-3), 3.46 – 3.31
m, 3H), 3.12 (ddd, J = 4.0, 8.0, 12.0 Hz, 2H). 13C NMR (125 MHz, D
O): δ
1
(a) F. Arcamone, F. Bizioli, Gazz. Chim. Ital. 1957, 87, 896 – 902 (2-
trehalosamine 1). (b) L. A. Dolak, T. M. Castle, A. L. Laborde, J. Antibiot.
3
(
2
1980, 33, 690 – 698 (3-trehalosamine 2). (c) S. Hanessain, P. Lavalee, J.
9
6
6
3
4.5 (C-1), 93.3 (C-1), 72.1 (C-3), 71.2 (C-4), 70.7 (C-2), 68.4 (C-5),
Antibiot. 1972, 25, 683 – 684 (6-trehalsomine 3). (d) H. Naganawa, N,
Usui, T. Takita, M. Hamada, K. Maeda, H. Umezawa, J. Antibiot. 1974,
27, 145 – 146 (4-trehalosamine 4). (e) T. Tsuno, C. Ikeda, K.-I. Numata,
K. Tomita, M. Konishi, M. Kawaguchi, J. Antibiot. 1986, 34, 1001–1003
8.36 (C-5), 67.8 (C-4), 67.4 (C-2), 54.5 (C-3), 40.5 (C-6 or C-6), 40.2 (C-
+
or C-6). HRMS (ESI): calcd for C12
62.1526 [M + Na] .
H
25
N
3
NaO
8
, 362.1534; found:
+
(
3,3-neotrehalsomine 8).
For trehalosyl 2,4,6-triamine 7, R
f
0.18 (iPrOH/NH
OH, 2/1); [훼]20 +128.0
4
D
2
M. L. De Bona, M. L. Giuffrida, F. Caraci, A. Copani, B. Pignataro, F.
1
(
2
c 0.75, H O); H NMR (500 MHz, D O): δ 5.47 (d, J = 3.5 Hz, 1H, H-1),
2
Attanasio, S. Cataldo, G. Pappalardoc, J. Peptide Sci. 2008, 15, 220 –
5
4
.25 (d, J = 3.5 Hz, 1H, H-1ʹ), 4.22 (t, J = 10.0 Hz, 1H, H-3), 4.18 (dt, J =
.0, 10.5 Hz, 1H, H-5), 3.86 – 3.75 (m, 4H), 3.68 (dd, J = 4.0, 10.5 Hz, 1H,
2
28.
A. Venot, E. E. Swayze, R. H. Griffey, G. J. Boons, ChemBioChem, 2004,
, 1228 – 1236.
3
4
H-2ʹ), 3.55 (dd, J = 3.5, 10.5 Hz, 1H, H-2), 3.43 – 3.33 (m, 3H, including H-
, H-4ʹ, and H-6aʹ), 3.16 (dd, J = 7.5, 13.5 Hz, 1H, H-6bʹ). 13C NMR (125
MHz, D
O): δ 93.5 (1JCH = 173 Hz, C-1ʹ), 90.9 (1JCH = 175 Hz, C-1), 71.3,
0.7, 69.9 (C-2ʹ), 68.6, 68.5, 65.5 (C-3), 59.8 (C-6), 53.3 (C-2), 52.1 (C-4),
5
4
(a) M. R. Narouz, S. E. Soliman, R. W. Bassily, R. I. El-Sokkary, A. Z.
Nasr, M. A. Nashed, Synlett, 2013, 24, 2271 – 2273. (b) N. Asano, K.
Katayama, M. Kameda, J. Antibiot. 1989, 42, 585 – 590 (3-trehalosamine
2
7
4
3
12 26 3 8
C H N O
+, 340.1709; found:
0.0 (C-6ʹ). HRMS (ESI): calcd for
40.1714 [M + H]+.
2
). (c) K. Sode, E. Akaike, H. Sugiura, W. Tsugawa, FEBS Letters, 2001,
4
89, 42 – 45 (trehalose derivatives by enzyme). (d) R. W. Bassily, R. I. EI-
Sokkary, B. A. Silwanis, A. S. Nematalla, M. A. Nashed, Carbohydr. Res.
1993, 239, 197 – 207 (trehalosamine analogues). (e) H. H. Baer, A. J. Bell,
Carbohydr. Res. 1979, 75, 175 – 184 (3-trehalosamine 2). (f) R. C. Garcia,
L. Hough, A. C. Richardson, Carbohydr. Res. 1990, 200, 307 – 317 (4-
f 4
For neotrehalosyl 3,3-diamine 8, R 0.2 (iPrOH/NH
D
OH, 2/1); [훼]20 +173.0
1
(
c 0.3, CH
3
OH); H NMR (600 MHz, CD
3
OD): δ 5.33 (d, J = 3.6 Hz, 1H, H-
3
1), 4.80 (d, J = 8.4 Hz, 1H, covered by the signal of D
2
O but the J values
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