J
G. St-Pierre et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3): δ = 7.67–7.61 (m, 4 H), 7.44–7.32 (m, 6 H),
6.73 (d, J = 2.1 Hz, 1 H), 6.66–6.60 (m, 2 H), 5.88 (dd, J = 8.8, 1.1 Hz, 2
H), 5.33 (d, J = 1.4 Hz, 1 H, H-1), 4.02 (t, J = 5.9 Hz, 1 H, H-4), 3.94 (d, J =
1.4 Hz, 1 H, H-2), 3.89–3.87 (m, 2 H, H-3, H-5), 3.85 (dd, J = 10.6, 5.0
Hz, 1 H, H-6), 3.80 (dd, J = 10.6, 7.0 Hz, 1 H, H-6), 0.99 (s, 9 H).
13C NMR (100 MHz, CDCl3): δ = 152.0, 148.3, 143.32, 135.8, 135.7,
133.0, 132.8, 130.08, 130.05, 128.0, 127.9, 109.4, 108.3, 101.5, 100.2,
98.9, 77.4, 71.4, 70.67, 69.8, 63.9, 26.9, 19.3.
HRMS-ESI: m/z (M + Na)+ calcd for C40H47NO10SiNa: 752.2861; found:
752.2873 (+1.55 ppm).
Phenyl 6-O-tert-butyldiphenylsilyl-α-D-glucopyranoside (8a)
White foam (18.7 mg, 80%, 9.2:1, α/β); [α]D25 +48.9 (c 0.08, CHCl3).
IR (neat): 3345, 3065, 3010, 2926, 2856, 1495, 1428, 1112, 1075 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.69–7.62 (m, 4 H), 7.45–7.27 (m, 8 H),
7.08–7.00 (m, 3 H), 5.51 (d, J = 3.8 Hz, 1 H, H-1), 3.96 (dt, J = 12.4, 6.2
Hz, 1 H, H-4), 3.89–3.85 (m, 2 H, 2 × H-6), 3.82–3.77 (m, 1 H, H-5),
3.75–3.67 (m, 2 H, H-2, H-3), 1.04 (s, 9 H).
HRMS-ESI: m/z (M + Na)+ calcd for C29H34O8SiNa: 561.1915; found:
561.1910 (–0.84 ppm).
13C NMR (100 MHz, CDCl3): δ = 156.6, 135.8, 135.7, 133.1, 133.0,
130.02, 130.00, 129.8, 127.94, 127.89, 123.0, 117.1, 97.3, 74.8, 72.3,
71.8, 71.6, 64.3, 27.0, 19.4.
HRMS-ESI: m/z (M + Na)+ calcd for C28H34O6SiNa: 517.2017; found:
517.2024 (+1.30 ppm).
2-Naphthyl 6-O-tert-butyldiphenylsilyl-α-D-galactopyranoside
(7j)
White foam (20.4 mg, 83%, 8.4:1, α/β); [α]D25 +100.2 (c 0.06, CHCl3).
IR (neat): 3360, 3052, 3013, 2930, 2891, 2856, 1600, 1511, 1467,
1427, 1106 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.76 (dd, J = 16.0, 8.5 Hz, 2 H), 7.69–
7.59 (m, 6 H), 7.47–7.27 (m, 8 H), 7.22 (dd, J = 8.9, 2.5 Hz, 1 H), 5.74 (d,
J = 3.7 Hz, 1 H, H-1), 4.23 (d, J = 3.2 Hz, 1 H, H-4), 4.10 (dd, J = 9.8, 3.7
Hz, 1 H, H-2), 4.03 (dd, J = 9.8, 3.2 Hz, 1 H, H-3), 3.98–3.87 (m, 3 H, H-
5, 2 × H-6), 1.00 (s, 9 H).
13C NMR (125 MHz, CDCl3): δ = 154.5, 135.8, 135.6, 134.4, 132.94,
132.85, 130.03, 130.00, 129.7, 128.0, 127.91, 127.90, 127.8, 127.4,
126.6, 124.6, 118.9, 111.4, 97.8, 71.5, 70.8, 69.9, 69.8, 64.0, 26.9, 19.2.
4-Methoxyphenyl 6-O-tert-butyldiphenylsilyl-α-D-glucopyrano-
side (8b)
White foam (17.6 mg, 80%, 6.6:1, α/β); [α]D25 +32.0 (c 0.05, CHCl3).
IR (neat): 3374, 3058, 2929, 2853, 1508, 1464, 1428, 1216, 1113, 1039
cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.68–7.64 (m, 4 H), 7.46–7.32 (m, 6 H),
6.98 (d, J = 9.1 Hz, 2 H), 6.77 (d, J = 9.1 Hz, 2 H), 5.38 (d, J = 3.8 Hz, 1 H,
H-1), 3.94 (t, J = 8.7 Hz, 1 H, H-4), 3.89–3.87 (m, 2 H, 2 × H-6), 3.86–
3.82 (m, 1 H, H-5), 3.76 (s, 3 H), 3.69 (dd, J = 9.4, 1.7 Hz, 1 H, H-3), 3.64
(dd, J = 9.4, 3.8 Hz, 1 H, H-2), 1.05 (s, 9 H).
HRMS-ESI: m/z (M + Na)+ calcd for C32H36O6SiNa: 567.2173; found:
567.2166 (–1.31 ppm).
13C NMR (125 MHz, CDCl3): δ = 155.5, 150.6, 135.8, 135.7, 133.13,
133.05, 130.01, 130.00, 127.94, 127.90, 118.6, 114.8, 98.4, 74.8, 72.3,
71.8, 71.6, 64.4, 55.8, 27.0, 19.4.
HRMS-ESI: m/z (M + Na)+ calcd for C29H36O7SiNa: 547.2122; found:
547.2134 (+2.10 ppm).
1-Naphthyl 6-O-tert-butyldiphenylsilyl-α-D-galactopyranoside
(7k)
White foam (21.3 mg, 83%, 8.2:1, α/β); [α]D25 +59.3 (c 0.06, CHCl3).
IR (neat): 3420, 3050, 2940, 2867, 1429, 1273, 1083 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.21–8.13 (m, 1 H), 7.87–7.81 (m, 1 H),
7.67–7.56 (m, 4 H), 7.55–7.27 (m, 10 H), 7.16 (d, J = 7.7 Hz, 1 H), 5.81
(d, J = 1.2 Hz, 1 H, H-1), 4.27–4.22 (m, 1 H, H-4), 4.18–4.15 (m, 2 H, H-
2, H-3), 3.98–3.86 (m, 3 H, H-5, 2 × H-6), 1.01 (s, 9 H).
13C NMR (100 MHz, CDCl3): δ = 152.1, 135.8, 135.6, 134.5, 133.0,
132.8, 130.03, 130.00, 128.0, 127.90, 127.88, 126.6, 126.1, 125.9,
125.8, 122.23, 121.4, 109.1, 97.6, 71.6, 70.8, 70.00, 69.95, 63.9, 26.9,
19.2.
4-Fluorophenyl 6-O-tert-butyldiphenylsilyl-α-D-glucopyranoside
(8c)
White foam (15.4 mg, 76%, 5.1:1, α/β), [α]D25 +11.4 (c 0.06, CHCl3).
IR (neat): 3394, 3078, 3010, 2930, 2860, 1504, 1428, 1202, 1112, 1075
cm–1
.
1H NMR (700 MHz, CDCl3): δ = 7.65 (d, J = 7.1 Hz, 4 H), 7.46–7.31 (m, 6
H), 7.02–6.98 (m, 2 H), 6.95–6.91 (m, 2 H), 5.41 (d, J = 3.7 Hz, 1 H, H-
1), 3.94 (t, J = 9.4 Hz, 1 H, H-4), 3.87 (d, J = 4.5 Hz, 2 H, 2 × H-6), 3.78
(dt, J = 9.4, 4.5 Hz, 1 H, H-3), 3.71–3.65 (m, 2 H, H-2, H-5), 1.05 (s, 9 H).
HRMS-ESI: m/z (M + Na)+ calcd for C32H36O6SiNa: 567.2173; found:
567.2176 (+0.49 ppm).
13C NMR (175 MHz, CDCl3): δ = 158.7 (d, J = 240.9 Hz), 152.7 (d, J = 2.4
Hz), 135.81, 135.71, 133.1, 133.00, 130.1, 130.0, 128.0, 127.9, 118.6
(d, J = 8.1 Hz), 116.2 (d, J = 23.2 Hz), 98.1, 74.7, 72.2, 71.8, 71.7, 64.3,
27.0, 19.4.
Methyl N-(benzyloxycarbonyl)-O-(6-O-tert-butyldiphenylsilyl-α-
D-galactopyranosyl)-L-tyrosinate (7l)
White foam (18.6 mg, 70%, 7.3:1, α/β); [α]D25 +68.2 (c 0.1, CHCl3).
IR (neat): 3389, 3017, 2931, 2858, 1723, 1510, 1428, 1218, 1112, 1077
HRMS-ESI: m/z (M + Na)+ calcd for C28H33FO6SiNa: 535.1923; found:
535.1937 (+2.69 ppm).
cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.69–7.61 (m, 4 H), 7.46–7.29 (m, 11
H), 6.99–6.95 (m, 4 H), 5.53 (d, J = 3.7 Hz, 1 H, H-1), 5.20 (d, J = 8.1 Hz,
1 H, NH), 5.09 (s, 2 H), 4.62 (dt, J = 8.1, 5.9 Hz, 1 H), 4.20 (d, J = 2.9 Hz,
1 H, H-4), 4.01 (dd, J = 9.0, 3.7 Hz, 1 H, H-2), 3.97–3.87 (m, 4 H, H-3, H-
5, 2 × H-6), 3.70 (s, 3 H), 3.11–2.98 (m, 2 H), 1.03 (s, 9 H).
13C NMR (100 MHz, CDCl3): δ = 172.1, 156.2, 155.8, 135.81, 135.77,
135.70, 135.65, 133.0, 132.8, 130.5, 130.1, 130.0, 128.7, 128.4, 128.2,
127.94, 127.90, 117.2, 98.0, 71.4, 70.6, 69.8, 69.7, 67.1, 63.9, 55.0,
52.5, 37.5, 26.9, 19.2.
4-Chlorophenyl 6-O-tert-butyldiphenylsilyl-α-D-glucopyranoside
(8d)
White foam (12.4 mg, 76%, 6.8:1, α/β); [α]D25 +46.6 (c 0.07, CHCl3).
IR (neat): 3355, 3072, 3010, 2928, 2856, 1489, 1428, 1228, 1113,
1034, 824 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.66–7.62 (m, 4 H), 7.46–7.33 (m, 6 H),
7.20 (d, J = 9.0 Hz, 2 H), 6.97 (d, J = 9.0 Hz, 2 H), 5.45 (d, J = 3.8 Hz, 1 H,
H-1), 3.95 (t, J = 8.9 Hz, 1 H, H-4), 3.86 (dd, J = 3.9, 1.9 Hz, 2 H, 2 × H-
6), 3.75–3.66 (m, 3 H, H-2, H-3, H-5), 1.04 (s, 9 H).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–N