S. Kopitzki et al. / Tetrahedron 69 (2013) 10621e10636
10635
acetyl-
-glucopyranoside (55). Obtained from reaction of allyl glycoside 47
(553 mg, 502 mol) with compound 16 (1.04 g, 5.00 mmol) and
a
-
L
-rhamnopyranosyl)-6-O-tert-butyldiphenylsilyl-2-deoxy-
b
-
GrubbseHoveyda second generation catalyst (17 mg, 27
m
mol) as
D
a colorless solid (255 mg, 199
m
mol, 74%). Rf¼0.42 (EE); mp 173 ꢁC;
20
m
[a
]
ꢀ6.9 (c 0.5, CHCl3); 1H NMR (500 MHz, CDCl3):
¼7.80e7.61
d
D
GrubbseHoveyda second generation catalyst (31 mg, 50
m
mol) as
(m, 4H, Harom), 7.55e7.34 (m, 6H, Harom), 7.30 (d, 3JAr¼8.4 Hz, 2H, H-
a colorless solid (540 mg, 422
m
mol, 84%). Rf¼0.35 (EE); mp 166 ꢁC;
1
arom), 6.85 (d, 3JAr¼8.4 Hz, 2H, H-2arom), 5.96e5.82 (m, 2H, H-2bu,
20 þ5.7 (c 0.25, CHCl3); 1H NMR (500 MHz, CDCl3):
¼7.81e7.70
d
H-3bu), 5.70 (d, J2, HNAc¼8.5 Hz, 1H, HNAc), 5.38 (d, J3 ,4 ¼3.5 Hz,
3
3
00 00
[
a]
D
(m, 4H, Harom), 7.48e7.35 (m, 6H, Harom), 7.31 (d, 3JAr¼8.1 Hz, 2H, H-
1H, H-400), 5.33e5.30 (m, 2H, H-40, Hacetal), 5.27 (dd, J3 ,4 ¼3.5
3
00 00
3
3
3
3
3
3
00
00
00 00
00 00
1
arom), 6.84 (d, JAr¼8.1 Hz, 2H, H-2arom), 6.15 (s, 1H, HNHAc),
J2 ,3 ¼10.0 Hz, 1H, H-3 ) 5.20 (d, J1 ,2 ¼3.7 Hz, 1H, H-1 ), 5.09 (d,
3
00
00 00
5.97e5.82 (m, 2H, H-2bu, H-3bu), 5.33 (s, 1H, Hacetal), 5.31 (d,
J1,2¼8.0 Hz, 1H, H-1), 4.95 (q, J5 ,6 ¼6.6 Hz, 1H, H-5 ), 4.93 (dd,
3 3
3
3
3
00
0
J3 ,4 ¼3.4 Hz,1H, H-4 ), 5.25 (dd, J2 ,3 ¼3.5,0 J3 ,4 ¼9.9 Hz,1H, H-3 )
J1 ,2 ¼8.1, J2 ,3 ¼10.4 00 Hz, 1H, H-20), 4.91 (dd, J1 ,2 ¼3.7,
00 00
0
0
0
0
0
0
0
0
00 00
3
3
3
3
5.19 (dd, J1 ,2 ¼1.8, J2 ,3 ¼3.5 Hz, 1H, H-2 ), 5.12 (dd, J3 ,4 ¼9.9,
J2 ,3 ¼10.0 Hz,1H, H-2 ), 4.76 (dd, J3,4¼9.4, 3J2,3¼10.0 Hz,1H, H-3),
0
0
0
0
0
0
00 00
3
3
3
3
3
J4 ,5 ¼9.9 Hz, 1H, H-4 ), 5.06 (dd, J1 ,2 ¼1.8, J2 ,3 ¼10.5 Hz, 1H, H-
4.71 (dd, 3J3 ,4 ¼3.3, J2 ,3 ¼10.4 Hz, 1H, H-3 ), 4.49 (d, J1 ,2 ¼8.1, 1H,
0
0
0
0
0
0
00 00
0
0
0
0
0
0
3
3
2
200), 4.93 (dd, J3 ,4 ¼0 3.4, J2 ,3 ¼10.5 Hz, 1H, H-3 ), 4.90 (d,
H-10) 4.42 (dd, J6 ab¼12.0, 3J5 ,6a ¼6.5 Hz, 1H, H-6a ), 4.38e4.32 (m,
00
0
00 00
00 00
0
0
0
3
3
J1 ,2 ¼1.8 Hz, 1H, H-1 ), 4.84 (d, J1,2¼7.4 Hz, 1H, H-1), 4.80 (d,
2H, H-6b0, H-1abu), 4.12e4.05 (m, 2H, H-2, H-1bb3u), 4.00 (dd,
0
0
3J1,2¼8.1 Hz, 1H, H-100), 4.50e4.48 (m, 2H, H-4bu), 4.46 (qd,
3J3,4¼9.4, J4,5¼9.4 Hz, 1H, H-4), 3.93 (dd, J6ab¼11.9, J5,6a¼2.9 Hz,
1H, H-6a), 3.65e3.60 (m, 2H, H-6b, H-50), 3.56e3.50 (m, 1H, H-5),
3.28 (s, 6H, OCH3), 2.15 (s, 3H, HAc), 2.11 (s, 3H, HAc), 2.08 (s, 3H,
3
2
3
3
0
0
0
0
0
J5 ,6 ¼6.1, J4 ,5 ¼9.9 Hz, 1H, H-5 ), 4.35e4.20 (m, 3H, H-3, H-6a,
1abu), 4.13e4.07 (m, 2H, H-6b, H-1bbu), 4.06e3.94 (m, 3H, H-4, H-
600ab), 3.79 (dd, 3J5,6a¼6.8, 3J5,6b¼6.8 Hz, 1H, H-5), 3.53e3.42 (m, 1H,
H-2), 3.33e3.25 (m, 7H, H-500, OCH3), 2.15 (s, 3H, HAc), 2.10 (s, 3H,
H
Ac), 2.05 (s, 3H, HAc), 2.02 (s, 3H, HAc), 1.99 (s, 3H, HAc), 1.95 (s, 3H,
3
00
00 00
H
Ac), 1.87 (s, 3H, HAc), 1.22 (d, J5 ,6 ¼6.6 Hz, 3H, H-6 ), 1.10 (s, 9H,
H
Ac), 2.02 (s, 6H, 2ꢂHAc), 1.98 (s, 9H, 3ꢂHAc), 1.92 (s, 3H, HAc), 1.25
SiC(CH3)3) ppm; 13C NMR (126 MHz, CDCl3):
d
¼170.9e169.4
3
(d, J5 ,6 ¼6.1 Hz, 3H, H-6 ), 1.07 (s, 9H, SiC(CH3)3) ppm; 13C NMR
(CH3CO), 136.3e127.0 (Carom), 114.8 (C-2bu), 114.3 (C-3bu), 102.6
(Caectal), 101.2 (C-100), 97.1 (C-10), 96.5 (C-1), 76.7 (C-3), 74.5 (C-5)
74.0 (C-4), 72.8 (C-300), 72.2 (C-40), 71.2 (C-50), 70.9 (C-200), 69.0 (C-
0
0
0
(101 MHz, CDCl3):
d¼172.1e168.8 (CH3CO), 136.8e127.4 (Carom),
115.0 (C-2bu), 114.1 (C-3bu), 101.9 (Caectal), 99.4 (C-100), 98.1 (C-10),
97.7 (C-1), 75.7 (C-3), 75.0 (C-5), 74.4 (C-4), 71.1 (C-40), 70.7 (C-500),
70.6 (C-300), 70.1 (C-30), 69.3 (C-1all), 68.9 (C-20), 68.7 (C-200), 68.0 (C-
1
bu), 68.8 (C-4bu), 68.6 (C-500), 67.4 (C-20), 66.7 (C-30), 64.3 (C-400),
62.3 (C-6), 60.8 (C-60), 59.2 (C-2), 52.1 (OCH3), 26.7 (SiC(CH3)),
24.0e20.3 (CH3CO), 19.1 (SiC(CH3)), 15.8 (C-600) ppm; HRMS (ESI):
calcd for C63H83NO25SiNaþ: 1304.4916, found: 1304.4974 [MþNa]þ.
4
bu), 67.6 (C-1bu), 67.0 (C-400), 66.3 (C-50), 62.1 (C-600), 61.5 (C-6), 54.9
(C-2), 53.1 (OCH3), 29.6 (C-60), 27.1 (SiC(CH3)), 23.7e19.9 (CH3CO),
19.3 (SiC(CH3)) ppm; HRMS (ESI): calcd for C63H83NO25SiNaþ:
1304.4916, found: 1304.4910 [MþNa]þ.
4.6.7. (E)-4-(4-Dimethoxymethylphenoxy)-but-2-enyl 2-acetamido-
4-O-(2,3,4,6-tetra-O-acetyl-
phenylsilyl-2-deoxy-3-O-(2,3,4-tri-O-acetyl-
glucopyranoside (58). Obtained from reaction of allyl glycoside 51
(340 mg, 310 mol) with compound 16 (583 mg, 2.80 mmol) and
b
-
L
-galactopyranosyl)-6-O-tert-butyldi-
4.6.5. (E)-4-(4-Dimethoxymethylphenoxy)-but-2-enyl 2-acetamido-
a-
D
-fucopyranosyl)-b-D-
4-O-(2,3,4,6-tetra-O-acetyl-
phenylsilyl-2-deoxy-3-O-(2,3,4-tri-O-acetyl-
glucopyranoside (56). Obtained from reaction of allyl glycoside 42
(185 mg, 168 mol) with compound 16 (315 mg, 1.51 mmol) and
b
-
D
-galactopyranosyl)-6-O-tert-butyldi-
b
-
L
-fucopyranosyl)-
b
-
D
-
m
GrubbseHoveyda second generation catalyst (19 mg, 31 mmol) as
m
a colorless solid (218 mg, 170
m
mol, 55%). Rf¼0.41 (EE); mp 175 ꢁC;
GrubbseHoveyda second generation catalyst (11 mg, 17
m
mol) as
[
a
]
20 þ22.3 (c 0.5, CHCl3); 1H NMR (500 MHz, CDCl3):
¼7.78e7.65
d
D
a colorless solid (169 mg, 132
m
mol, 79%). Rf¼0.42 (EE); mp 179 ꢁC;
(m, 4H, Harom), 7.45e7.31 (m, 8H, Harom), 6.91 (d, 3JAr¼8.3 Hz, 2H, H-
20 þ2.6 (c 0.25, CHCl3); 1H NMR (500 MHz, CDCl3):
d
¼7.80e7.57
2
arom), 5.96e5.80 (m, 2H, H-2bu, H-3bu), 5.73 (d, JNH,2¼8.2 Hz, 1H,
3
[
a
]
D
(m, 4H, Harom), 7.55e7.29 (m, 8H, Harom), 6.85 (d, 3JAr¼8.0 Hz, 2H, H-
NHAc), 5.40 (d, J1 ,2 ¼3.0 Hz, 1H, H-1 ), 5.36 (dd, J4 ,5 ¼0.5,
3
3
0
0
0
0
0
3
00
J3 ,4 ¼3.3 Hz, 1H, H-4 ), 5.29 (s, 1H, Hacetal), 5.22e4.99 (m, 4H, H-20,
0
0
2
arom), 6.10 (s, 1H, HNAc), 5.93e5.79 (m, 2H, H-2bu, H-3bu), 5.35e5.31
3
(m, 2H, H-400, Hacetal), 5.21 (d, J3 ,4 ¼3.3 Hz, 1H, H-4 ), 5.08 (dd,
H-40, H-50, H-200), 4.95e4.88 (m, 2H, H-30, H-300), 4.81 (d,
0
0
0
3
3
3
3
3
3
J1 ,2 ¼8.0, J2 ,3 ¼10.5 Hz, 1H, H-200), 5.00 (dd, J3 ,4 ¼3.3,
J1,2¼8.5 Hz, 1H, H-1), 4.75 (d, J1 ,2 ¼7.8 Hz, 1H, H-1 ), 4.51e4.47
00
00 00
00 00
0
0
00 00
3
0
0
0
0
3
0
0
J2 ,3 ¼10.5, 3.44 Hz, 1H, H-3 ), 4.95 (d, J1 ,2 ¼8.1 Hz, 1H, H-1 ), 4.91
(m, 2H, H-4bu) 4.38e4.35 (m, 1H, H-1abu), 4.17e4.05 (m, 3H, H-
600a,b, H-1bbu), 4.02 (dd, 3J4,5¼9.3, 3J3,4¼9.9 Hz, 1H, H-4), 3.96e3.78
3
3
00
00 00
00 00
(dd, J3 ,4 ¼3.1, J2 ,3 ¼10.5 Hz, 1H, H-3 ), 4.88 (d, J1,2¼7.8 Hz, 1H,
3
3
3
00
H-1), 4.62 (d, J1 ,2 ¼8.0 Hz, 1H, H-1 ), 4.50e4.47 (m, 2H, H-4bu),
(m, 4H, H-3, H-6ab, H-500), 3.55 (ddd, J2,NH¼8.2, J1,2¼8.5,
3J2,3¼9.9 Hz, 1H, H-2), 3.44 (ddd, 3J5,6a¼5.3, 3J5,6b¼6.2, 3J4,5¼9.3 Hz,
1H, H-5), 3.27 (s, 6H, OCH3), 2.16 (s, 3H, HAc), 2.15 (s, 3H, HAc), 2.10
(s, 3H, HAc), 2.08 (s, 3H, HAc), 2.06 (s, 3H, HAc), 2.03 (s, 3H, HAc), 1.99
00 00
4.38e4.26 (m, 2H, H-3, H-1abu), 4.13e4.08 (m, 2H, H-600), 4.10e4.00
(m, 2H, H-4, H-1bbu), 3.94e3.89 (m, 2H, H-6), 3.82 (q, 3J5 ,6 ¼6.1 Hz,
0
0
3
3
1H, H-50), 3.65 (dd, J1,2¼8.0, J2,030¼9.5 Hz, 1H, H-2), 3.57 (dd,
3
3
J5 ,6a ¼6.7, J5 ,6a ¼6.7 Hz, 1H, H-5 ), 3.40e3.30 (m, 1H, H-5), 3.28
(s, 3H, HAc), 1.72 (s, 3H, HAc), 1.28 (d, 3J5 ,6 ¼6.5 Hz, 3H, H-6 ), 1.07 (s,
0
00
00
00
00
0
0
(s, 6H, OCH3), 2.17 (s, 3H, HAc), 2.13 (s, 3H, HAc), 2.04 (s, 6H, 2ꢂHAc),
9H, SiC(CH3)3) ppm; 13C NMR (126 MHz, CDCl3):
d
¼171.0e168.2
2.03 (s, 3H, HAc), 2.00 (s, 3H, HAc), 1.95 (s, 3H, HAc), 1.91 (s, 3H, HAc),
(CH3CO), 136.6e127.0 (Carom), 114.4 (C-2bu), 114.3 (C-3bu), 103.2 (C-
10), 102.7 (Caectal), 101.9 (C-100), 99.5 (C-1), 79.9 (C-40), 79.3 (C-4),
76.8 (C-30), 76.3 (C-3), 75.7 (C-5), 72.6 (C-30), 72.2 (C-500), 71.4 (C-200),
70.3 (C-20), 69.9 (C-1all), 69.3 (C-400), 69.0 (C-4bu), 68.8 (C-50), 68.8
(C-4bu), 68.0 (C-1bu), 62.5 (C-6), 62.0 (C-600), 54.8 (C-2), 52.5 (OCH3),
26.6 (SiC(CH3)), 24.0e20.3 (CH3CO), 19.2 (SiC(CH3)), 16.0 (C-
60) ppm; HRMS (ESI): calcd for C63H83NO25SiNaþ: 1304.4916,
found: 1304.4941 [MþNa]þ.
1.22 (d, J5 ,6 ¼6.1 Hz, 3H, H-6 ), 1.09 (s, 9H, SiC(CH3)3) ppm; 13C
3
0
0
0
NMR (126 MHz, CDCl3):
d
¼171.4e168.4 (CH3CO), 136.5e126.8
(Carom), 114.1 (C-2bu), 113.8 (C-3bu), 102.5 (Caectal), 100.1 (C-10), 99.2
(C-1), 98.9 (C-100), 75.2 (C-5), 74.6 (C-3), 74.2 (C-4), 71.2 (C-30), 70.7
(C-500), 70.4 (C-40), 70.3 (C-300), 69.6 (C-20), 69.2 (C-50), 69.0 (C-200),
68.8 (C-4bu), 67.5 (C-1bu), 66.5 (C-400), 62.6 (C-6), 60.5 (C-600), 54.4
(C-2), 52.5 (OCH3), 29.4 (C-60), 26.7 (SiC(CH3)), 23.4e20.1 (CH3CO),
19.1 (SiC(CH3)) ppm; HRMS (ESI): calcd for C63H83NO25SiNaþ:
1304.4916, found: 1304.4936 [MþNa]þ.
References and notes
4.6.6. (E)-4-(4-Dimethoxymethylphenoxy)-but-2-enyl 2-acetamido-
3-O-(2,3,4,6-tetra-O-acetyl-
phenylsilyl-2-deoxy-4-O-(2,3,4-tri-O-acetyl-
glucopyranoside (57). Obtained from reaction of allyl glycoside 49
(296 mg, 268 mol) with compound 16 (500 mg, 2.41 mmol) and
b
-
D
-galactopyranosyl)-6-O-tert-butyldi-
a
-
L
-fucopyranosyl)-
b-D-
m