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Fmoc-C -H), 7.30 (t, J=7.4 Hz, 2 H, Fmoc-C -H), 7.36–
3,6
2,7
H-2, H-2’), 7.39–7.29 (m, 5 H, arenes), 7.28 (d, J=8.2 Hz,
2 H, H-3, H-3’), 5.26 (d, J=6.9 Hz, 1 H, Boc-NH), 5.10 (s,
2 H, CH2 ), 4.28–4.21 (m, 1 H, H-a), 2.40 (s, 3 H, aryl-
7
5
.27 (m, 5 H, arenes), 5.98 (d, J=8.2 Hz, 1 H, Fmoc-NH),
.24 (t, J=9.4 Hz, 1 H, H-3), 5.23 (s, 2 H, CH2 ), 5.06 (t,
Bn
Bn
J=9.7 Hz, 1 H, H-4), 5.01 (t, J=8.7 Hz, 1 H, H-2), 4.76–
.69 (m, 1 H; H-a), 4.47 (d, J=7.6 Hz, 1 H, H-1), 4.45
CH ), 2.36–2.25 (m, 2 H, H-g, H-g’), 2.15–2.07 (m, 1 H, H-
3
13
4
b), 1.88–1.79 (m, 1 H, H-b’), 1.43 (s, 9 H, C(CH ) );
C
3
3
1
0
(
1
4
dd, J=7.2, 10.8 Hz, 1 H, Fmoc-C -Ha), 4.34–4.28 (m,
NMR (150.9 MHz, CDCl ): d=171.6 (C(O)OBn), 170.0
3
10
H, Fmoc-C -Hb), 4.28 (dd, J=12.4, 5.0 Hz, 1 H, H-6a),
(C(O)NHSO ), 156.1 (NHC(O)Ot-Bu), 144.8, 135.8, 134.9
2
9
arene
arene
.22 (t, J=7.1 Hz, 1 H, Fmoc-C -H), 4.16–4.10 (m, 2 H,
(quart C
), 129.5 (C-2), 128.6 (C
(C(CH ) ) 67.5 (CH ), 52.6 (C-a), 32.5 (C-g), 28.4 (C-b),
), 128.4 (C-1), 80.7
Bn
H-6b, H-1’a), 3.99 (ddd, J=10.4, 10.3, 2.4 Hz, 1 H, H-1’b),
3
3
2
3
1
4
2
3
.79–3.70 (m, 1 H, H-2’a), 3.70 (ddd, J=9.8, 4.9, 1.8 Hz,
H, H-5), 3.46–3.40 (m, 1 H, H-2’b), 3.15 (dd, J=17.1,
.2 Hz, 1 H, H-b), 3.00 (dd, J=16.9, 3.0 Hz, 1 H, H-b’),
.08 (s, 3 H, C(O)CH ), 2.06 (s, 3 H, C(O)CH ), 2.03 (s,
27.9 (C(CH ) ), 21.5 (aryl-CH ); MALDI-MS calcd. for
3 3 3
+
C H N O SNa [M+Na] m/z: 513.2, found: 513.1; anal.
2
4
30
2
7
calcd. for C H N O S: C 58.76, H 6.16, N 5.71; found: C
2
4
30
2
7
58.73, H 6.12, N 5.77.
3
3
1
3
H, C(O)CH ), 2.00 (s, 3 H, C(O)CH ); C NMR
Boc-Gln(b-D-glucopyranosyl-oxyethylsulfonyl)-OMe
(24): Boc-Gln(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl-
oxyethylsulfonyl)-OBn 17 (128 mg, 0.17 mmol) was dis-
solved in a 0.5 M solution of NaOMe in MeOH (1 mL).
After 5 min, the solution was neutralized with acidic ion
exchange resin (DOWEX 50 WX8) and the solvent was
evaporated. RP-HPLC of an aliquot gave pure 24 (94%)
3
3
(150.9 MHz, CDCl ): d=171.6, 171.1, 170.0, 169.4 (C=O),
3
arene
156.1 (NHC(O)OFm), 143.8–135.1 (quart C
), 128.6,
arene
128.4, 128.3, 127.7, 127.1, 120.0 (C
), 100.7 (C-1), 72.2
Bn
(C-5), 72.1 (C-3), 71.3 (C-2), 68.2 (C-4), 67.8 (CH2 ),
67.4 (C-10), 64.0 (C-1’), 61.7 (C-6), 52.1 (C-2’), 50.3 (C-a),
47.0 (C-9), 38.2 (C-b), 20.9, 20.7, 20.5 (C(O)CH );
3
+
MALDI-MS calcd. for C H N O SNa [M+Na] m/z:
as a white solid. RP-HPLC (): R =8.3 min (10–85% B in
4
2
46
2
17
t
1
9
5
05.2, found: 905.1; anal. calcd. for C H N O S: C
7.14, H 5.25, N 3.17; found: C 57.38, H 5.54, N 3.01.
20 min); H NMR (600 MHz, [D] -acetone): d=4.37 (d,
4
2
46
2
17
6
J=7.8 Hz, 1 H, H-1), 4.24–4.15 (m, 2 H, H-1’a, H-a), 4.04
(ddd, J=12.0, 7.8, 4.5 Hz, 1 H, H-1’b), 3.83 (dd, J=11.8,
1.8 Hz, 1 H, H-6a), 3.77–3.71 (m, 1 H, H-2’a), 3.69–3.64
Fmoc-Asn(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl-
oxyethylsulfonyl)-OBn (20): Sulfonyl azide 7 (46 mg,
.09 mmol), Fmoc-Asp(SH)-OBn 14 (74 mg, 0.13 mmol),
0
(m, 1 H, H-6b), 3.69 (s, 3 H, OCH ), 3.66–3.60 (m, 1 H,
3
and 2,6-lutidine (15 mL, 0.13 mmol) were reacted in dry
H-2’b), 3.40 (t, J=8.5 Hz, 1 H, H-3), 3.36–3.30 (m, 2 H,
H-4, H-5), 3.19 (t, J=8.4 Hz, 1 H, H-2), 2.60–2.50 (m,
2 H, H-g, H-g’), 2.19–2.10 (m, 1 H, H-b), 1.99–1.91 (m,
CHCl (1.5 mL) for 15 min, according to GP2. FC (petro-
3
leum ether/EtOAc, 2 :1 ! EtOAc) gave 20 (71 mg, 89%)
13
as a white solid. R =0.14 (petroleum ether/EtOAc, 1:2);
1 H, H-b’), 1.40 (s, 9 H, C(CH ) ); C NMR (150.9 MHz,
f
3 3
1
H NMR (600 MHz, CDCl ): d=8.97 (s, 1 H, SO NH),
.76 (d, J=7.5 Hz, 2 H, Fmoc-C -H), 7.60 (d, J=7.4 Hz,
H, Fmoc-C -H), 7.40 (t, J=7.4 Hz, 2 H, Fmoc-C -H),
.36–7.27 (m, 7 H, arenes, Fmoc-C -H), 6.00 (d, J=
.4 Hz, 1 H, Fmoc-NH), 5.39 (d, J=3.1 Hz, 1 H, H-4),
[D] -acetone): d=174.1, 173.4, 157.3 (C=O), 105.3 (C-1),
3
2
6
4
,5
7
2
7
8
5
1
78.6 (C-3), 78.4 (C-5), 75.4 (C-2), 72.1 (C-4), 65.6 (C-1’),
1
,8
3,6
63.3 (C-6), 54.6 (C-a), 53.7 (C-2’), 53.2 (OCH ), 33.9 (C-
3
2
,7
g), 29.4 (C(CH ) ), 27.8 (C-b); ESI-MS calcd. for
3
3
À
C H N O S [MÀH] m/z: 529.2, found: 529.1.
1
9
33
2
13
Bn
.25 (d, J=12.3 Hz, 1 H, CHaHb ), 5.22 (d, J=12.0 Hz,
H, CHaHb ), 5.15 (dd, J=10.3, 7.9 Hz, 1 H, H-2), 5.04
Fmoc-Asp(STrt)-OBn
(26):
Fmoc-Asp-OBn
10
Bn
(150 mg, 0.34 mmol), triphenylmethanethiol (188 mg,
0.68 mmol), and 4-(dimethylamino)pyridine (2 mg,
0.03 mmol) were dissolved in dry CH Cl (1.7 mL) and
(
4
dd, J=10.4, 3.3 Hz, 1 H, H-3), 4.72–4.68 (m, 1 H, H-a),
.45 (d, J=7.9 Hz, 1 H, H-1), 4.47–4.40 (m, 1 H, Fmoc-
2
2
1
0
10
C -Ha), 4.37–4.26 (m, 1 H, Fmoc-C -Hb), 4.26–4.19 (m,
cooled to 08C. A solution of N,N’-dicyclohexylcarbodi-
9
2
4
6
1
H, H-6a, Fmoc-C -H), 4.19–4.13 (m, 1 H, H-1’a), 4.07–
.01 (m, 1 H, H-6b), 4.04–3.98 (m, 1 H, H-1’b), 3.90 (t, J=
.4 Hz, 1 H, H-5), 3.81–3.74 (m, 1 H, H-2’a), 3.46–3.40 (m,
H, H-2’b), 3.20 (dd, J=17.1, 4.5 Hz, 1 H; H-b), 3.02 (dd,
imide (76 mg, 0.37 mmol), in dry CH Cl (0.3 mL), was
2
2
added dropwise, and the resulting suspension was stirred
for 3.5 h, during which the temperature was gradually in-
creased to rt. The suspension was filtered, concentrated,
and purified by FC (petroleum ether/EtOAc, 5 :1) to give
J=17.0, 3.4 Hz, 1 H, H-b’), 2.10 (s, 3 H, C(O)CH ), 2.09
3
(
s, 3 H, C(O)CH ), 2.05 (s, 3 H, C(O)CH ), 2.00 (s, 3 H,
26 (202 mg, 85%) as a white solid. R =0.68 (petroleum
3
3
f
1
C(O)CH ); MALDI-MS calcd. for C H N O SNa [M+
Na] m/z: 905.2, found: 905.1.
Boc-Gln(4-methylbenzenesulfonyl)-OBn (22): 4-Meth-
ylbenzenesulfonyl azide 21 (49 mg, 0.25 mmol), Boc-
Glu(SH)-OBn 13 (157 mg, 0.38 mmol), and 2,6-lutidine
ether/EtOAc, 1:1); H NMR (600 MHz, CDCl ): d=7.77
3
42 46
2
17
3
+
4,5
(t, J=7.9 Hz, 2 H, Fmoc-C -H), 7.59 (d, J=7.0 Hz, 2 H,
Fmoc-C -H), 7.41 (m, 2 H, Fmoc-C -H), 7.35–7.19 (m,
22 H, arenes, Fmoc-C -H), 5.58 (d, 1 H, NH), 5.16 (d,
J=12.3 Hz, 1 H, CH2 ), 5.08 (d, J=12.3 Hz, 1 H, CH2 ),
4.68–4.54 (m, 1 H, H-a), 4.42 (dd, J=7.3, 10.4 Hz, 1 H,
1
,8
3,6
2
,7
Bn
Bn
(
44 mL, 0.38 mmol) were reacted in dry MeOH (4 mL)
1
0
10
for 3 h, according to GP2. FC (petroleum ether/EtOAc,
3
0
Fmoc-C -Ha), 4.37 (dd, J=7.3, 10.4 Hz, 1 H, Fmoc-C -
Hb), 4.22 (t, J=7.0 Hz, 1 H, Fmoc-C -H), 3.27 (dd, J=
9
:1!1:1) gave 22 (119 mg, 96%) as a white solid. R =
f
1
.39 (petroleum ether/EtOAc, 1:1); H NMR (600 MHz,
16.8, 4.8 Hz, 1 H, H-b), 3.25 (dd, J=17.3, 4.2 Hz, 1 H, H-
13
CDCl ): d=9.57 (s, 1 H, SO NH), 7.92 (d, J=8.0 Hz, 2 H,
b’); C NMR (150.9 MHz, CDCl ): d=194.8 (C(O)STrt),
3
2
3
Isr. J. Chem. 2015, 55, 437 – 446
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
444