LETTER
Glucosamine Building Blocks
2715
(6) Rai, R.; McAlexander, I.; Chang, C. W. T. Org. Prep.
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H, OH). 13C NMR (100 MHz, CDCl3, 23 °C): d = 54.4, 68.2,
69.8, 70.2, 71.9, 73.6, 74.4, 74.5, 80.1, 95.3, 96.8, 117.9,
127.6, 127.7, 128.4, 128.5, 133.3, 137.7, 138.2, 154.1.
HRMS–FAB: m/z calcd for C26H30NCl3O7: 574.1166;
found: 574.1152.
Compound (8): white solid. 1H NMR (400 MHz, CDCl3, 23
°C): d = 7.40–7.26 (m, 12 H, ArH), 7.05 (d, 2 H, J = 7.5 Hz,
ArH), 5.11 (br s, 1 H, NH), 4.90 (d, 1 H, J = 9.7 Hz, H-1),
4.76 (s, 4 H, 2 × CH2Ph), 4.57 (dd, 2 H, J = 11.8, 18.2 Hz,
CH2CCl3), 3.80–3.75 (m, 3 H, 3-H, 2 × H-6), 3.67 (t, 1 H,
J = 9.0 Hz, H-4), 3.52–3.50 (m, 1 H, H-5), 3.35 (dd, 1 H,
J = 9.0 Hz, 17.6 Hz, H-2), 2.78 (br s, 1 H, OH), 2.30 (s, 3 H,
SPhCH3).
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Y.-W.; Lee, C.-C.; Chang, K.-L.; Hung, S.-C. Nature
(London) 2007, 446, 896.
25
Compound (10): colorless solid; mp 176–179 °C; [a]D
+43.3 (c 0.12, CHCl3). 1H NMR (400 MHz, CDCl3, 23 °C):
d = 7.49–7.26 (m, 20 H, ArH), 5.89–5.80 (m, 1 H,
CH2CH=CH2), 5.42 (s, 1 H, CHPh), 5.28–5.20 (m, 2 H,
CH2CH=CH2), 4.95–4.55 (m, 10 H, H-1, 2 × CH2Ph,
CH2Ph, 2 × CH2CCl3), 4.29 (d, 1 H, J = 12.1 Hz, CH2Ph),
4.13–3.95 (m, 5 H, CH2CH=CH2, H-2, H-1¢, H-3¢), 3.76–
3.44 (m, 6 H, H-6¢, H-2¢, H-4¢, H-3, H-5, H-6), 3.20–3.11 (m,
3 H, H-4, H-5¢, H-6¢). 13C NMR (100 MHz, CDCl3, 23 °C):
d = 54.6, 57.4, 65.4, 66.8, 68.4, 68.5, 70.2, 73.6, 73.9, 74.5,
76.5, 77.7, 78.0, 82.1, 95.4, 95.5, 96.7, 100.9, 101.1, 118.2,
126.0, 127.2, 127.8, 128.2, 128.3, 128.4, 129.0, 129.8,
133.2, 137.2, 137.7, 138.2, 138.9, 154.0, 154.1. HRMS
(ESI-TOF): m/z calcd for C49H52Cl6N2O13Na: 1109.1492;
found: 1109.1493.
(17) Wang, C.-C.; Kulkarni, S. S.; Lee, J.-C.; Luo, S.-Y.; Hung,
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(25) All steps involved were previously investigated separately in
order to obtain the authentic intermediates samples, to
support the TLC monitoring.
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(42) General Procedure for the Isomerization
To a solution of compound 5 or 11 (0.14 mmol) and Pd(PPh3)4
(8 mg, 5 mol%) in dry CH2Cl2 (3.2 mL) was added TES (27
mL, 0.17 mmol). After stirring for 24 h at r.t., the reaction
mixture was quenched with sat. aq solution of NaHCO3 (1
mL) and extracted with CH2Cl2. The organic layer was
washed with brine (1 mL), dried over Na2SO4, and
(27) Selected Spectroscopic Data
Compound (7): white solid; mp 63–65 °C; [a]D25 +58.8 (c
0.5, CHCl3). 1H NMR (400 MHz, CDCl3, 23 °C): d = 7.49–
7.26 (m, 10 H, ArH), 5.90 (m, 1 H, CH2CH=CH2), 5.23 (d, 1
H, J = 17.4 Hz, CH2CH=CH2), 5.24 (d, 1 H, J = 10.1 Hz,
CH2CH=CH2), 5.16 (d, 1 H, J = 9.7 Hz, NH), 4.80–4.70 (m,
3 H, H-1, CH2CCl3), 4.67–4.54 (m, 4 H, CH2Ph), 4.17 (m, 1
H, CH2CH=CH2), 4.01–3.98 (m, 2 H, H-2, CH2CH=CH2),
3.70–3.60 (m, 5 H, H-4, H-5, H-6a, H-6b, H-3), 2.66 (br s, 1
Synlett 2010, No. 18, 2711–2716 © Thieme Stuttgart · New York