F
J.-S. Chen et al.
Paper
Synthesis
1H NMR (CDCl3, 400 MHz): = 4.48 (d, J = 7.6 Hz, 1 H), 3.72 (m, 2 H),
3.58 (dd, J = 9.4, 8.6 Hz, 1 H), 3.24 (dd, J = 9.8, 8.6 Hz, 1 H), 3.14–3.06
(m, 2 H), 0.93 (s, 9 H), 0.19 (s, 9 H), 0.15 (s, 6 H), 0.14 (s, 9 H), 0.10 (s, 9
H).
1H NMR (CDCl3, 400 MHz): = 4.82 (d, J = 3.2 Hz, 1 H), 3.79 (m, 1 H),
3.74 (dd, J = 7.8, 2.6 Hz, 1 H), 3.61 (t, J = 2.8 Hz, 1 H), 3.60–3.56 (m, 1
H), 3.50 (dd, J = 11.2, 8.4 Hz, 1 H), 0.13 (s, 9 H), 0.12 (s, 18 H), 0.10 (s, 9
H).
13C NMR (CDCl3, 100 MHz): = 97.3, 76.7, 76.5, 71.4, 69.9, 61.6, 25.6,
13C NMR (CDCl3, 100 MHz): = 95.6, 74.3, 72.6, 68.5, 64.0, 0.4, 0.3,
17.9, 0.9, 0.7, –0.4, –4.3, –5.3.
0.02, –0.2.
HRMS (ESI): m/z [M + Na]+ calcd for C21H49N3O5Si4Na: 558.2647;
HRMS (ESI): m/z [M + Na]+ calcd for C17H43O5Si4Na: 461.2007; found:
found: 558.2648.
461.2011.
2-Deoxyl-4-methylphenyl-2-phthalimido-1-thio-3,4,6-tri-O-
trimethylsilyl--D-glucopyranoside (2h)
1,2,3,5-Tetra-O-trimethylsilyl-D-ribofuranoside (2k)
Prepared according to the general procedure 1; colorless oil; yield:
582.5 mg (96%); / = 1:2; Rf = 0.65 (EtOAc/ hexane 1:22); []D
–16.833 (c 1.2, DCM).
29
Prepared according to the general procedure 1; white solid; yield:
279.3 mg (92%); mp 123–125 °C; Rf = 0.35 (EtOAc/hexane 1:9); []D
29
+46.7 (c 1.0, DCM).
1H NMR (CDCl3, 400 MHz): = 4.85 (d, J = 3.6 Hz, 0.52 H), 4.75 (d, J =
7.2 Hz, 1 H), 3.99 (t, J = 10.4 Hz, 0.74 H), 3.87 (s, 0.54 H), 3.87 (s, 1 H),
3.68 (s, 0.68 H), 3.67 (d, J = 2.8 Hz, 1 H), 3.65–3.59 (m, 1 H), 3.52–3.44
(m, 1 H), 3.42–3.40 (t, J = 3.4 Hz, 0.55 H), 3.22 (dd, J = 7.2, 3.2 Hz, 1 H),
3.20–3.16 (m, 0.66 H), 0.14 (s, 9 H), 0.12 (s, 6 H), 0.12 (s, 9 H), 0.11 (s,
9 H), 0.10 (s, 9 H), 0.10 (s, 8 H), 0.09 (s, 4 H).
1H NMR (CDCl3, 400 MHz): = 7.99 (d, J = 22.4 Hz, 2 H), 7.88 (s, 2 H),
7.42–7.37 (m, 2 H), 7.14 (d, J = 8 Hz, 2 H), 5.58 (d, J = 10 Hz, 1 H), 4.54
(t, J = 9.2 Hz, 1 H), 4.31 (t, J = 10.2 Hz, 1 H), 3.94 (dt, J = 11.6, 7.2 Hz, 3
H), 3.83 (t, J = 9.0 Hz, 1 H), 3.52 (d, J = 7.8 Hz, 1 H), 2.42 (s, 3 H), 0.32 (s,
9 H), 0.29 (s, 9 H), 0.01 (s, 9 H).
13C NMR (CDCl3, 100 MHz): = 137.7, 134.1, 132.8, 131.9, 129.4,
13C NMR (CDCl3, 100 MHz): = 94.7, 92.6, 74.9, 73.8, 73.6, 70.6, 63.8,
123.6, 123.12, 83.7, 80.7, 74.7, 72.5, 61.8, 56.8, 21.1, 0.84, 0.76, –0.2.
58.1, 0.5, 0.4, 0.3, –0.02, –0.06, –0.18.
HRMS (ESI): m/z [M + Na]+ calcd for C30H45NO6SSi3Na: 654.2173;
HRMS (ESI): m/z [M]+ calcd for C17H43O5Si4: 439.2188; found:
found: 654.2177.
439.2187.
1,2,3,5-Tetra-O-trimethylsilyl--D-xylofuranoside (2i)
1,2,3,5-Tetra-O-trimethylsilyl--D-arabinofuranoside (2l)
Prepared according to the general procedure 1; white solid; yield:
581.3 mg (99%); mp 36–38 °C; only; Rf = 0.49 (EtOAc/hexane 1:22);
[]D30 +69.8 (c 1.0, DCM).
Prepared according to the general procedure 1; colorless oil; yield:
531.2 mg (91%); only; Rf = 0.45 (EtOAc/hexane 1:22); []D29 –54.33
(c 1.0, DCM).
1H NMR (CDCl3, 400 MHz): = 4.93 (d, J = 3.2 Hz, 1 H), 3.69 (t, J = 8.4
Hz, 1 H), 3.64 (t, J = 10.0 Hz, 1 H), 3.53–3.46 (m, 1 H), 3.43 (dd, J = 10.2,
5.4 Hz, 1 H), 3.34 (dd, J = 9.0, 3.0 Hz, 1 H), 0.15 (s, 9 H), 0.13 (s, 9 H),
0.12 (s, 18 H).
13C NMR (CDCl3, 100 MHz): = 94.2, 74.12, 74.07, 71.9, 62.3, 0.9, 0.4,
0.3, 0.2.
1H NMR (CDCl3, 400 MHz): = 4.95 (d, J = 2.4 Hz, 1 H), 3.86–3.82 (m, 1
H), 3.73–3.63 (m, 3 H), 3.43 (dd, J = 11.2, 5.6 Hz, 1 H), 0.07 (s, 9 H),
0.06 (s, 9 H), 0.05 (s, 9 H), 0.05 (s, 9 H).
13C NMR (CDCl3, 100 MHz): = 94.0, 71.3, 70.0, 64.1, 0.2, 0.1, –0.1.
HRMS (ESI): m/z [M]+ calcd for C17H43O5Si4: 439.2188; found:
439.2186.
HRMS (ESI): m/z [M]+ calcd for C17H43O5Si4: 439.2188; found:
439.2183.
Methyl-4,6-O-benzylidene-2,3-di-O-trimethylsilyl--D-glucopyra-
noside (2m)
1,2,3,5-Tetra-O-trimethylsilyl--D-lyxopyranoside (2j-1)
Prepared according to the general procedure 1; colorless oil; yield:
Prepared according to the general procedure 1; colorless oil; yield:
577.5 mg (99%); only; Rf = 0.44 (EtOAc/hexane 1:22); []D29 +20.636
(c 1.1, DCM).
1H NMR (CDCl3, 400 MHz): = 4.61 (s, 1 H), 3.91–3.84 (m, 1 H), 3.81
(dd, J = 11.2, 5.2 Hz, 1 H), 3.69–3.66 (m, 1 H), 3.36 (dd, J = 8.4, 2.8 Hz, 1
H), 3.06 (dd, J = 11.2, 9.6 Hz, 1 H), 0.14 (s, 9 H), 0.13 (s, 18 H), 0.10 (s, 9
H).
285 mg (94%); Rf = 0.37 (EtOAc/hexane 1:9); []D29 +44.5 (c 1.2, DCM).
1H NMR (CDCl3, 400 MHz): = 7.51–7.47 (m, 2 H), 7.38–7.32 (m, 3 H),
5.51 (s, 1 H), 4.62 (d, J = 3.6 Hz, 1 H), 4.27 (dd, J = 10, 4.6 Hz, 1 H), 3.96
(t, J = 9.0 Hz, 1 H), 3.80 (dd, J = 10, 4.8 Hz, 1 H), 3.71 (t, J = 10.2 Hz, 1
H), 3.62 (dd, J = 8.8, 4.0 Hz, 1 H), 3.42 (s, 3 H), 0.18 (s, 9 H), 0.10 (s, 9
H).
13C NMR (CDCl3, 100 MHz): = 128.8, 128.1, 126.1, 101.7, 101.0, 82.1,
74.1, 71.7, 69.1, 62.3, 55.4, 0.7, 0.3.
13C NMR (CDCl3, 100 MHz): = 95.7, 75.0, 74.6, 67.6, 66.1, 0.5, 0.3,
0.08, 0.02.
HRMS (ESI): m/z [M + Na]+ calcd for C20H34O6Si2Na: 449.1792; found:
449.1779.
HRMS (ESI): m/z [M + Na]+ calcd for C17H43O5Si4Na: 461.2007; found:
461.2011.
1,2,3,5-Tetra-O-trimethylsilyl--D-lyxofuranoside (2j-2)
Funding Information
Prepared according to the general procedure 2; colorless oil; yield:
577.7 mg (99%); only; Rf = 0.81 (EtOAc/hexane 1:18); []D29 +183.0
(c 1.0, DCM).
The authors thank the Ministry of Science and Technology (MOST) in
Taiwan (MOST 107-2113-M-005-021) and National Chung Hsing Uni-
versity for financial support.
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