A. J. Fairbanks et al.
(dd, 3J1a,2a =8.5, 3J2a,3a =10.5Hz, 1H; H-2a), 4.49–4.52 (m, 2H; H-3d,
PhCH), 4.56–4.60 (m, 4H; 4PhCH), 4.64 (d, 3J1b,2b =8.2 Hz, 1H; H-1b),
4.67 (d, 2J=11.7 Hz, 1H; PhCH), 4.72 (d, 3J1f,2f =1.6 Hz, 1H; H-1f), 4.78
(d, 2J=11.5Hz, 1H; PhCH), 4.81 (d, 2J=12.2 Hz, 1H; PhCH), 4.82 (d,
2J=12.6 Hz, 1H; PhCH), 4.90 (d, 2J=10.9 Hz, 1H; PhCH), 5.02 (dd,
3J2b,3b =9.4 Hz, 1H; H-2b), 5.07 (m, 2H; H-1d, H-2e), 5.13–5.14 (m, 2H;
3J1d,2d =1.5Hz, 1H; H-1d), 4.81 (d, 3J1f,2f =1.2 Hz, 1H; H-1f), 4.94 (d,
3J1e,2e =1.8 Hz, 1H; H-1e), 4.96 (dd, 3J2b,3b =9.5Hz, 1H; H-2b), 4.97 (d,
3J1c,2c =2.1 Hz, 1H; H-1c), 5.08 (dd, 3J2e,3e =3.3 Hz, 1H; H-2e), 5.12 (dd,
3J2c,3c =3.0 Hz, 1H; H-2c), 5.13 (at, 3J=9.6 Hz, 1H; H-4b), 5.18 (dd,
3J3e,4e =10.1 Hz, 1H; H-3e), 5.22–5.30 (m, 7H; H-1a, H-2d, H-2f, H-3f, H-
4d, H-4e, H-4f), 6.76–6.77 (m, 2H; 2Ar-H), 6.88–6.89 (m, 2H; 2Ar-
H), 7.10–7.12 (m, 2H; 2Ar-H), 7.21–7.36 ppm (m, 23H; 23Ar-H);
13C NMR (125.8 MHz, CDCl3): d=20.6, 20.7, 20.7, 20.8, 20.8, 20.9, 20.9,
21.1, 23.2 (9q, 14C(O)CH3), 51.6 (d, C-2a), 55.6 (q, OCH3), 62.0 (t,
C-6e), 62.4 (t, C-6f), 65.6 (d, C-4e), 65.9 (d, C-4f), 65.9 (t, C-6d), 66.4 (t,
C-6b), 67.5(d, C-4d), 68.5(t, C-6c), 68.6 (2d, C-3e, C-5f), 69.0 (t, C-
6a), 69.0 (t, C-2c), 69.0 (d, C-3f), 69.3 (d, C-5e), 69.4 (d, C-2d), 69.5 (d,
C-5d), 69.7 (d, C-2e), 70.1 (d, C-4b), 70.6 (d, C-2f), 71.9 (t, PhCH2), 72.1
(d, C-2b), 72.3 (d, C-5b), 72.3 (d, C-5c), 73.1, 73.4, 73.5 (3t, 3PhCH2),
73.6 (d, C-4c), 74.3 (d, C-5a), 74.9 (t, PhCH2), 75.1 (d, C-4a), 75.8 (d, C-
H-3e, H-4e), 5.20 (d, 3J1e,2e =1.6 Hz, 1H; H-1e), 5.22 (dd, 3J2f,3f =3.3 Hz,
3
1H; H-2f), 5.31 (at, 3J=10.2 Hz, 1H; H-4f), 5.41 (dd, 3J1c,2c =1.6, J2c,3c
=
3.0 Hz, 1H; H-2c), 5.44 (dd, 3J3f,4f =10.2 Hz, 1H; H-3f), 5.47 (d, 1H; H-
1c), 5.55 (dd, 3J1d,2d =1.5, 3J2d,3d =3.5Hz, 1H; H-2d), 5.65(d, 1H; H-1a),
5.66 (at, 3J=10.0 Hz, 1H; H-4d), 6.72–6.78 (m, 5H; 5Ar-H), 6.81–6.83
(m, 2H; 2Ar-H), 7.02–7.03 (m, 2H; 2Ar-H), 7.19–7.21 (m, 2H; 2
Ar-H), 7.32–7.46 (m, 19H; 19Ar-H), 7.55–7.58 (m, 4H; 4Ar-H), 7.63–
7.67 (m, 5H; 5Ar-H), 8.07–8.09 (m, 2H; 2Ar-H), 8.16–8.17 ppm (m,
2H; 2Ar-H); 13C NMR (125.8 MHz, CDCl3): d=20.5, 20.5, 20.6, 20.5,
20.7, 20.8, 20.8, 21.1 (8q, 10OCOCH3), 27.7 (t, CH2CH2C(O)CH3),
29.7 (q, CH2C(O)CH3), 37.5(t, CH 2CH2C(O)CH3), 55.5 (d, C-2a), 55.5
(q, OCH3), 62.0 (t, C-6e), 62.2 (t, C-6f), 65.8 (d, C-4f), 65.9 (d, C-4e),
66.2 (t, C-6d), 67.2 (t, C-6b), 67.7 (t, C-6a), 68.5(d, C-4d), 68.5(d, C-5f),
68.7 (d, C-3e), 68.7 (d, C-2c), 69.1 (d, C-2e), 69.2 (d, C-3f), 69.2 (d, C-5e),
69.4 (d, C-5d), 69.5(t, C-6c), 69.5(d, C-2f), 70.4 (d, C-4b), 71.4 (d, C-2b),
71.6 (d, C-5c), 71.8 (t, PhCH2), 72.0 (t, C-2d), 73.5(t, PhCH 2), 73.6 (t,
PhCH2), 74.3 (d, C-4c), 74.5(t, PhCH 2), 74.7 (d, C-5b), 74.9 (t, PhCH2),
75.1 (d, C-5a), 76.4 (d, C-3a), 76.5 (d, C-3d), 77.9 (d, C-4a), 78.2 (d, C-
3d), 76.0 (d, C-3a), 77.7 (d, C-3c), 79.4 (d, C-3b), 97.2 (d, 1J
174 Hz; C-1f), 97.4 (d, 1J(C,H)=174 Hz; C-1d), 98.6 (d, 1J
168 Hz; C-1a), 99.2 (d, 1J(C,H)=174 Hz; C-1e), 99.4 (d, 1J
174 Hz; C-1c), 99.5(d, 1J
(C,H)=161 Hz; C-1b), 114.4, 117.8, 127.4, 127.5,
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
AHCTREUNG
127.7, 127.7, 127.7, 127.8, 128.0, 128.1, 128.2, 128.3, 128.3, 128.3, 128.4,
128.4 (16d, 29Ar-C), 137.9, 137.9, 138.0, 138.3, 138.5, 151.2, 154.9 (7
s, 7Ar-C), 169.4, 169.6, 169.7, 169.8, 169.8, 170.0, 170.0, 170.2, 170.3,
170.4, 170.5, 170.5, 170.7 ppm (13s, 14C=O); IR (KBr): n˜ =3418 (br,
NH), 1751 cmꢀ1 (s, C=O); MS (ESI): species observed: [M+2Na]2+
(major); peaks observed: m/z (%): 1089.9 (85), 1090.4 (100), 1090.9 (41),
1091.4 (28), 1091.9 (8); calcd for: 1089.9 (86), 1090.4 (100), 1090.9 (67),
1091.4 (32), 1091.9 (14).
3c), 79.0 (d, C-3b), 96.2 (d, 1J
175Hz; C-1f), 97.4 (d, 1J(C,H)=175Hz; C-1d), 97.4 (d, 1J
167 Hz; C-1a), 99.9 (d, 1J(C,H)=175Hz; C-1e), 100.1 (d, 1J
ACHTREUNG
(C,H)=173 Hz; C-1c), 96.9 (d, 1J
ACHRTEUNG ACHTREUNG
A
ACHTREUNG
C
162 Hz; C-1b), 114.3, 118.5, 127.0, 127.5, 127.6, 127.7, 127.8, 127.9, 127.9,
128.0, 128.1, 128.2, 128.2, 128.3, 128.4, 128.4, 128.5, 128.7 (18d, 37Ar-
C), 129.0, 129.2 (2s, 2Ar-C), 130.0, 130.0, 133.2, 133.4 (4d, 6Ar-C),
137.7, 138.0, 138.1, 138.4, 138.5, 150.9, 155.2 (7s, 9Ar-C), 165.6, 165.7,
169.1, 169.2, 169.6, 169.9, 169.9, 170.6, 170.6, 171.4, 206.3 ppm (11s, 15
C=O); IR (KBr): n˜ =3487 (br, OH), 1714, 1751 cmꢀ1 (s, C=O); MS (ESI):
species observed: [M+Na]+ (major); peaks observed: m/z (%): 2382.9
(68), 2383.9 (100), 2384.9 (68), 2385.9 (24), 2386.9 (3); calcd for: 2382.8
(73), 2383.8 (100), 2384.8 (75), 2385.8 (40), 2386.8 (17).
p-Methoxyphenyl
2,3,4,6-tetra-O-acetyl-a-d-mannopyranosyl-(1!3)-
[2,3,4,6-tetra-O-acetyl-a-d-mannopyranosyl-(1!6)]-2,4-di-O-acetyl-a-d-
mannopyranosyl-(1!6)-2,4-di-O-acetyl-[2,3,4,6-tetra-O-acetyl-a-d-man-
nopyranosyl-(1!3)]-b-d-glucopyranosyl-(1!4)-3,6-di-O-acetyl-2-acetam-
ido-2-deoxy-b-d-glucopyranoside (44): Benzyl ether 43 (55 mg,
25.8 mmol) was dissolved in ethanol (5mL) and ethyl acetate (5mL). Pal-
ladium (10% on carbon, 20 mg) was added and the reaction mixture
stirred at room temperature under an atmosphere of hydrogen. After
21 h, TLC (ethyl acetate/methanol 8:2) indicated formation of a major
product (Rf =0.45) and complete consumption of starting material (Rf =
0.8). The reaction mixture was poured onto Celite, washed with ethanol
(310 mL) and ethyl acetate (310 mL), filtered and concentrated in
vacuo. The residue was dissolved in pyridine (2.5mL), the solution
cooled to 08C and acetic anhydride (2 mL) added. After 25h, TLC
(ethyl acetate) indicated formation of a single product (Rf =0.3) and
complete consumption of starting material (Rf =0.65). The reaction mix-
ture was poured onto ice/water (5mL) and extracted with CH 2Cl2 (2
5mL). The combined organic layers were washed with hydrochloric acid
(210 mL of a 1m solution), NaHCO3 (210 mL of a saturated solution),
dried (MgSO4), filtered and concentrated in vacuo. The residue was puri-
fied by flash column chromatography (ethyl acetate) to afford acetate 44
p-Methoxyphenyl
2,3,4,6-tetra-O-acetyl-a-d-mannopyranosyl-(1!3)-
[2,3,4,6-tetra-O-acetyl-a-d-mannopyranosyl-(1!6)]-2,4-di-O-acetyl-a-d-
mannopyranosyl-(1!6)-2,4-di-O-acetyl-[3,4,6-tri-O-benzyl-a-d-manno-
pyranosyl-(1!3)]-b-d-glucopyranosyl-(1!4)-2-acetamido-3,6-di-O-
benzyl-2-deoxy-b-d-glucopyranoside (43): Phthalimide protected hexasac-
charide 42 (1.02 g, 430 mmol) was dissolved in methanol (20 mL) and eth-
ylene diamine (11.5mL, 172 mmol) added. The solution was refluxed at
658C. After 3 d, the reaction mixture was concentrated in vacuo and the
residue dissolved in pyridine (15mL). The solution was cooled to 0 8C
and acetic anhydride (10 mL) added. After 1 d, TLC (petrol/ethyl acetate
1:3) indicated formation of a single product (Rf =0.3) and complete con-
sumption of starting material (Rf =0.5). The reaction mixture was poured
onto ice/water (50 mL) and extracted with CH2Cl2 (220 mL). The com-
bined organic layers were washed with hydrochloric acid (220 mL of a
(45.0 mg, 92%) as
a
white amorphous solid. [a]2D3 =+22 (c=0.2 in
CHCl3); 1H NMR (500 MHz, CDCl3): d=2.01, 2.03, 2.04, 2.08, 2.10, 2.10,
2.13, 2.15, 2.17, 2.18, 2.19, 2.21, 2.21, 2.22, 2.27 (15s, 57H; 19
C(O)CH3), 3.51 (brd, 2J6d,6’d =9.2 Hz, 1H; H-6d), 3.58 (dd, 3J5b,6b =1.8,
2J6b,6’b =11.6 Hz, 1H; H-6b), 3.61 (dat, 3J4b,5b =9.8, 3J=2.9 Hz, 1H; H-5b),
3.82 (s, 3H; OCH3), 3.83–3.92 (m, 6H; H-3b, H-4a, H-5a, H-5d, H-6’b,
H-6’d), 4.07 (dat, 3J4e,5e =10.2, 3J=2.7 Hz, 1H; H-5e), 4.09–4.18 (m, 4H;
H-5c, H-5f, H-6c, H-6e), 4.20 (dd, 3J5f,6f =2.2, 2J6f,6’f =12.3 Hz, 1H; H-6f),
4.26–4.35(m, 5H; H-2a, H-3d, H-6a, H-6 ’e, H-6’f), 4.36 (dd, 3J5c,6’c =4.7,
1m solution), NaHCO3 (220 mL of
a saturated solution), dried
(MgSO4), filtered and concentrated in vacuo. The residue was purified by
flash column chromatography (petrol/ethyl acetate 1:3) to afford acet-
amide 43 (755 mg, 82%) as an amorphous white foam. [a]2D3 =+33 (c=
0.5in CHCl 3); 1H NMR (700 MHz, CDCl3): d=1.93, 1.96, 1.96, 2.00,
2.02, 2.03, 2.05, 2.05, 2.10, 2.13, 2.14, 2.14, 2.15, 2.17 (14s, 42H; 14
C(O)CH3), 3.40 (dd, 3J5b,6b =2.3, 2J6b,6’b =10.7 Hz, 1H; H-6b), 3.43 (ddd,
2
3
2
3J4b,5b =10.1, 3J5b,6’b =4.8 Hz, 1H; H-5b), 3.53 (dd, 3J5d,6d =2.2, J6d,6’d
=
2J6c,6’c =12.2 Hz, 1H; H-6’c), 4.50 (dd, J5a,6’a =3.1, J6a,6’a =11.8 Hz, 1H; H-
6’a), 4.50 (d, 3J1b,2b =8.0 Hz, 1H; H-1b), 4.84 (d, 3J1d,2d =0.6 Hz, 1H; H-
1d), 4.89 (d, 3J1f,2f =1.0 Hz, 1H; H-1f), 4.96 (d, 3J1c,2c =1.7 Hz, 1H; H-1c),
5.06 (dd, 3J2b,3b =9.4 Hz, 1H; H-2b), 5.07 (d, 3J1a,2a =6.4 Hz, 1H; H-1a),
11.4 Hz, 1H; H-6d), 3.61 (brd, 2J6c,6’c =8.9 Hz, 1H; H-6c), 3.68–3.85(m,
12H; H-3b, H-5a, H-5c, H-5d, H-6a, H-6’a, H-6’b, H-6’c, H-6’d, OCH3),
3.89 (dd, 3J2c,3c =3.1, 3J3c,4c =9.5Hz, 1H; H-3c), 3.92–3.95 (m, 2H; H-3a,
H-4c), 3.96–4.01 (m, 3H; H-2a, H-4a, H-6e), 4.02 (ddd, 3J4e,5e =9.9,
3J5e,6e =2.3, 3J5e,6’e =4.8 Hz, 1H; H-5e), 4.07 (ddd, 3J4f,5f =9.6, 3J5f,6f =2.5,
3J5f,6 ’f =4.8 Hz, 1H; H-5f), 4.11 (dd, 2J6f,6’f =10.7 Hz, 1H; H-6f), 4.13 (dd,
3J2d,3d =3.4, 3J3d,4d =7.7 Hz, 1H; H-3d), 4.27 (dd, 1H; H-6’f), 4.28 (dd,
2J6e,6’e =12.2 Hz, 1H; H-6’e), 4.34, 4.65(ABq, 2J=12.0 Hz, 2H; PhCH2),
4.42 (d, 3J1b,2b =8.2 Hz, 1H; H-1b), 4.44, 4.81 (ABq, 2J=11.1 Hz, 2H;
3
3
5.14 (m, 3H; H-1e, H-2c, H-2e), 5.17 (dd, J2e,3e =3.2, J3e,4e =10.1 Hz, 1H;
3
3
H-3e), 5.21 (dd, J2a,3a =9.3, J3a,4a =10.2 Hz, 1H; H-3a), 5.23–5.36 (m, 8H;
H-2d, H-2f, H-3c, H-3f, H-4b, H-4c, H-4d, H-4f), 5.38 (at, 3J=10.0 Hz,
1H; H-4e), 6.13 (d, 3J2a,NH =9.4 Hz, 1H; NH), 6.84–6.86 (m, 2H; 2Ar-
H), 6.96–6.98 ppm (m, 2H; 2Ar-H); 13C NMR (125.8 MHz, CDCl3): d=
20.6, 20.6, 20.7, 20.7, 20.7, 20.8, 20.8, 20.9, 20.9, 20.9, 21.0 (11q, 18
OC(O)CH3), 23.2 (q, NC(O)CH3), 52.4 (d, C-2a), 55.6 (q, OCH3), 61.6 (t,
C-6e), 62.2 (t, C-6c), 62.3 (t, C-6f), 62.7 (t, C-6a), 65.1 (d, C-4e), 65.8 (2
2
2
PhCH2), 4.48, 4.50 (ABq, J=12.1 Hz, 2H; PhCH2), 4.50, 4.61 (ABq, J=
2
11.0 Hz, 2H; PhCH2), 4.70, 4.76 (ABq, J=11.7 Hz, 2H; PhCH2), 4.78 (d,
6460
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 6444 – 6464