5704
Y.-tao Zhao et al. / Tetrahedron 72 (2016) 5699e5706
1H), 3.66e3.60 (m, 2H), 2.35 (s, 3H), 2.04 (s, 3H). 13C NMR
(100 MHz, CDCl3) 170.6, 138.3, 138.2, 137.4, 132.4, 130.2, 129.6,
4.14. p-Methylphenyl 2,3,4-tri-O-methyl-1-thio-b-D-gal-
actopyranoside (7b)
d
128.4,128.3,128.1,127.8, 127.7, 127.6, 88.1, 84.3, 76.0, 75.7, 74.3, 73.4,
73.2, 68.0, 63.5, 21.1, 20.9.
General procedure A and B, colorless oil, 1H NMR (400 MHz,
CDCl3)
d
7.44 (d, 2H, J¼8.2 Hz), 7.10 (d, 2H, J¼8.0 Hz), 4.46 (d, 1H,
J¼9.6 Hz), 3.88e3.93 (m, 1H), 3.65e3.71 (m, 1H), 3.63 (d, 1H,
J¼2.4 Hz), 3.60 (s, 3H), 3.54 (s, 3H), 3.53 (s, 3H), 3.38e3.43 (m, 2H),
3.20 (dd, 1H, J¼3.0, 9.2 Hz), 2.32 (s, 3H), 2.06 (dd, 1H, J¼3.0, 9.1 Hz).
4.9. p-Methylphenyl 6-O-acetyl-2,3,4-tri-O-benzyl-1-thio-b-D-
mannopyranoside (4b)
13C NMR (100 MHz, CDCl3)
d 137.7,132.5,130.1,129.7, 88.1, 86.1, 79.4,
General procedure A, B and C, white solid, 85%; 1H NMR
(400 MHz, CDCl3)
78.9, 75.9, 62.4, 61.4, 61.3, 58.5, 21.2.
d
7.40e7.28 (m, 17H), 7.14 (d, 2H, J¼8.0 Hz), 5.54
(d, 1H, J¼1.4 Hz), 5.50 (d, 1H, J¼5.50 Hz), 4.76e4.62 (m, 5H),
4.38e4.36 (m, 3H), 4.04e3.98 (m, 2H), 3.94e3.91 (dd, 1H, J¼9.2,
4.15. p-Methylphenyl 2,6-di-O-acetyl-3,4-di-O-methyl-1-thio-
b-D
-galactopyranoside (7c)
3.0 Hz), 2.36 (s, 3H), 2.07 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 170.8,
138.1,138.0,137.9,132.3,130.2,129.8,128.5,128.4,128.1,127.9,127.8,
85.9, 80.1, 76.0, 75.3, 74.7, 72.1, 71.9, 70.9, 63.6, 21.1, 20.9.
General procedure A, B and C, white solid, 28%; 1H NMR
(400 MHz, CDCl3)
d
7.40 (d, 2H, J¼8.1 Hz), 7.09 (d, 2H, J¼8.1 Hz), 5.23
(t, 1H, J¼9.8 Hz), 4.53 (d, 1H, J¼10.0 Hz), 4.23e4.35 (m, 2H), 3.69 (d,
1H, J¼2.6 Hz), 3.63 (t, 1H, J¼6.3 Hz), 3.55 (s, 3H), 3.45 (s, 3H), 3.30
(dd,1H, J¼2.8, 9.6 Hz), 2.33 (s, 3H), 2.13 (s, 3H), 2.08 (s, 3H). 13C NMR
4.10. p-Methoxyphenyl 6-O-acetyl-2,3,4-tri-O-methyl-b-D-
glucopyranoside (5b)
(100 MHz, CDCl3)
d 170.7, 169.6, 137.7, 132.5, 130.1, 129.5, 87.3, 83.7,
General procedure A, B and C, white solid, 43%; 1H NMR
(400 MHz, CDCl3)
76.2, 74.9, 69.7, 63.3, 61.3, 58.2, 21.1, 21.1, 20.8.
d
6.99e7.05 (m, 4H), 4.79 (d, 1H, J¼9.2 Hz), 4.34
(dd,1H, J¼2.2,11.8 Hz), 4.23 (dd,1H, J¼6.1,11.8 Hz), 3.66 (s, 3H), 3.65
(s, 3H), 3.54 (s, 3H), 3.50e3.53 (m, 1H), 3.24e3.31 (m, 2H), 3.16 (t,
1H, J¼9.2 Hz), 2.28 (s, 3H), 2.07 (s, 3H). 13C NMR (100 MHz, CDCl3)
4.16. p-Methylphenyl 3,6-di-O-acetyl-2,4-di-O-methyl-1-thio-
b-D-galactopyranoside (7d)
General procedure A, B and C, white solid, 8%; 1H NMR
(400 MHz, CDCl3)
d
155.0, 122.5, 118.0, 101.9, 86.5, 83.6, 79.6, 73.1, 63.4, 61.1, 60.8, 21.2,
21.0.
d
7.46 (d, 2H, J¼8.1 Hz), 7.10 (d, 2H, J¼8.0 Hz), 4.85
(dd, 1H, J¼3.0, 9.7 Hz), 4.50 (d, 1H, J¼9.7 Hz), 4.31 (dd, 1H, J¼6.9,
11.2 Hz), 4.17 (dd, 1H, J¼6.0, 11.2 Hz), 3.66 (m, 2H), 3.54 (s, 3H), 3.51
4.11. p-Methoxyphenyl 2,6-di-O-acetyl-3,4-di-O-methyl-b-D-
glucopyranoside (5c)
(d, 1H, 9.7 Hz), 3.48 (s, 3H), 2.33 (s, 3H), 2.16 (s, 3H), 2.06 (s, 3H). 13
C
NMR (100 MHz, CDCl3)
d170.7, 170.5, 137.9, 132.7, 130.0, 129.7, 88.3,
General procedure A, B and C, white solid, 18%; 1H NMR
(400 MHz, CDCl3) 6.92e6.94 (m, 2H), 6.79e6.81 (m, 2H), 5.11 (dd,
77.3, 77.3, 76.8, 75.7, 62.7, 61.5, 61.2, 21.3, 21.2, 20.9.
d
4.17. p-Methoxyphenyl 2,3,4-tri-O-methyl-b-D-galactopyrano-
side (8b)
1H, J¼8.0, 9.2 Hz), 4.80 (d, 1H, J¼7.9 Hz), 4.39 (dd, 1H, J¼2.2,
11.8 Hz), 4.25 (dd, 1H, J¼5.6, 11.9 Hz), 3.77 (s, 3H), 3.56 (s, 3H), 3.55
(s, 3H), 3.53e3.54 (m, 1H), 3.29e3.41 (m, 2H), 2.14 (s, 3H), 2.09 (s,
General procedure A and B, colorless oil; 1H NMR (400 MHz,
DMSO) 6.99e7.02 (m, 2H), 6.90e6.93 (m, 2H), 4.88 (d, 1H,
3H). 13C NMR (100 MHz, CDCl3)
d 170.9, 151.4, 118.6, 114.6, 100.4,
d
84.8, 79.4, 73.3, 72.9, 63.1, 60.8, 60.5, 55.8, 21.1, 21.0.
J¼5.2 Hz), 4.84 (d, 1H, J¼7.2 Hz), 3.77 (d, 1H, J¼2.1 Hz), 3.76 (s, 3H),
3.56e3.60 (m, 2H), 3.55 (s, 3H), 3.50 (s, 3H), 3.47 (s, 3H), 3.36 (d, 3H,
J¼14.0 Hz). 13C NMR (100 MHz, CDCl3)
d
155.3, 151.5, 118.5, 114.6,
4.12. p-Methoxyphenyl 3,6-di-O-acetyl-2,4-di-O-methyl-b-D-
glucopyranoside (5d)
102.9, 84.0, 80.6, 75.6, 75.2, 62.2, 61.4, 61.1, 58.7, 55.8.
General procedure A, B and C, white solid, 16%; 1H NMR
(400 MHz, CDCl3) 6.98e7.01 (m, 2H), 6.81e6.84 (m, 2H), 5.16 (t,
4.18. p-Methoxyphenyl 2,6-di-O-acetyl-3,4-di-O-methyl-b-D-
galactopyranoside (8c)
d
1H, J¼9.3 Hz), 4.83 (d, 1H, J¼7.7 Hz), 4.36 (dd, 1H, J¼2.2, 11.9 Hz),
4.27 (dd, 1H, J¼5.7, 11.9 Hz), 3.78 (s, 4H), 3.60 (s, 3H), 3.43 (s, 3H),
3.33 (t, 2H, J¼9.2 Hz), 2.17 (s, 3H), 2.09 (s, 1H). 13C NMR (100 MHz,
General procedure A, B and C, white solid, 41%; 1H NMR
(400 MHz, CDCl3) 6.94e6.96 (m, 2H), 6.78e6.81 (m, 2H), 5.43 (dd,
d
CDCl3)
d 170.7, 170.0, 155.5, 151.1, 118.6, 118.5, 114.5, 102.4, 83.4,
1H, J¼7.9, 10.0 Hz), 4.79 (d, 1H, J¼7.8 Hz), 4.27e4.39 (m, 2H), 3.77 (s,
83.0, 81.2, 77.9, 75.5, 72.7, 63.0, 60.6, 60.0, 55.7, 21.1, 20.9, 20.8,
20.8.
3H), 3.71e3.73 (m, 2H), 3.61 (s, 3H), 3.49 (s, 3H), 3.36 (dd, 1H, J¼2.8,
10.0 Hz), 2.11 (s, 3H), 2.10 (s, 3H). 13C NMR (100 MHz, CDCl3)
d170.8,
155.5, 151.6, 118.8, 114.5, 100.9, 82.5, 74.6, 72.7, 71.1, 63.1, 61.4, 58.4,
55.8, 21.1, 21.0.
4.13. p-Methylphenyl 2,6-di-O-acetyl-3, 4-di-O-benzyl-1-thio-
b-D
-glucopyranoside (6b)
4.19. p-Methoxyphenyl 3,6-di-O-acetyl-2,4-di-O-methyl-b-D-
galactopyranoside (8d)
General procedure A, B and C, white solid, 85%; 1H NMR
(400 MHz, CDCl3)
d
7.43e7.28 (m, 12H), 7.09 (d, 2H, J¼8.0 Hz),
5.45e5.40 (t, 1H, J¼9.8 Hz), 5.0 (d, 1H, J¼11.7 Hz), 4.74 (d, 1H,
J¼12.1 Hz), 4.63e4.54 (m, 3H), 4.31e4.26 (dd, 1H, J¼11.2, 7.0 Hz),
4.14e4.10 (dd, 1H, J¼11.3, 5.4 Hz), 3.88 (d, 1H, J¼2.0 Hz), 3.64e3.57
(m, 2H), 2.33 (s, 3H), 2.09 (s, 3H), 2.01 (s, 3H). 13C NMR (100 MHz,
General procedure A, B and C, white solid, 15%; 1H NMR
(400 MHz, CDCl3) 7.00e7.02 (m, 2H), 6.80e6.82 (m, 2H), 4.87 (dd,
1H, J¼3.1, 10.2 Hz), 4.78 (d, 1H, J¼7.7 Hz), 4.35 (dd, 1H, J¼6.7,
11.1 Hz), 4.20 (dd,1H, J¼6.3,11.1 Hz), 3.77 (s, 3H), 3.67e3.75 (m, 2H),
3.63 (s, 3H), 3.53 (s, 3H), 2.18 (s, 3H), 2.08 (s, 3H). 13C NMR
d
CDCl3)
d 170.6, 169.5, 138.0, 137.7, 132.6, 129.7, 129.5, 128.5, 128.3,
128.2, 127.9, 127.7, 127.5, 87.0, 81.7, 76.2, 74.2, 72.5, 72.4, 69.7, 63.4,
21.1, 21.1, 20.8.
(100 MHz, CDCl3)
76.3, 75.3, 72.1, 62.4, 61.6, 61.1, 55.8, 21.2, 20.9.
d170.7, 170.6, 155.6, 151.4, 118.9, 114.6, 103.0, 78.3,