LETTER
First N-Glycosylated Indoxyls
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Baratte, B.; Kunick, C.; Parzy, D.; Pearl, L.; Doerig, C.;
Meijer, L. Biochim. Biophys. Acta 2004, 1697, 181.
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being studied. Preliminary results suggest that different is-
atins and N-glycoslyated indoxyls can be successfully
employed.
Acknowledgement
Financial support by the State of Mecklenburg-Vorpommern
(scholarship for S.L.) is gratefully acknowledged.
References and Notes
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Indoxyl-3-acetates
Silver acetate (6.0 equiv) was added to a stirred solution of
3-iodoindolylrhamnoside in glacial acetic acid. The
resulting suspension was stirred at 80 °C for 4 h. After the
reaction was completed, the solution was allowed to cool to
r.t., and ice water was subsequently added. The suspension
was filtered, and the filtrate was extracted with EtOAc (3×).
The combined organic layers were washed with an aq
solution of NaHCO3 and H2O and dried over Na2SO4. The
solution was filtered and the solvent of the filtrate was
removed under reduced pressure. The residue was purified
by column chromatography.
3-Acetoxy-1-(2¢,3¢,4¢-tri-O-benzyl-b-L-rhamnopyranosyl)
indole (8b)
Starting with 6b (2.30 g, 3.5 mmol), AcOH (20 mL), and
AgOAc (3.50 g, 21.0 mmol), 8b was isolated after column
chromatography (heptanes–EtOAc = 10:1 → 6:1) as
22
colorless crystals (1.23 g, 60%), mp 125–126 °C; [a]D
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–24.24 (c 1.13, CHCl3); Rf = 0.36 (heptanes–EtOAc = 3:1).
1H NMR (250 MHz, CDCl3): d = 7.66 (s, 1 H, H-2); 7.54 (m,
3J = 7.6 Hz, 1 H, Hetar), 7.39–7.10 (m, 18 H, Hetar, Ph),
5.55 (d, 3J1¢,2¢ = 0.9 Hz, 1 H, H-1¢), 5.01, 4.73 (2 d,
2JHa,Hb = 10.9 Hz, 2 H, CH2Ph), 4.68 (s, 2 H, CH2Ph), 4.41,
4.26 (2d, 2JHa,Hb = 11.1 Hz, 2 H, CH2Ph), 4.00 (‘dd’,
3J1¢,2¢ = 0.9 Hz, 3J2¢,3¢ = 2.4 Hz, 1 H, H-2¢), 3.80–3.75 (m,
3J2¢,3¢ = 2.3 Hz, 3J4¢,5¢ = 9.3 Hz, 2 H, H-3¢, H-4¢), 3.67–3.55
(m, 3J5¢,6¢ = 6.1 Hz, 3J4¢,5¢ = 9.3 Hz, 1 H, H-5¢), 2.36 [s, 3 H,
C(O)CH3], 1.42 (d, 3J5¢,6¢= 6.1 Hz, 1 H, H-6¢). 13C NMR (75
MHz, CDCl3): d = 168.4 [C(O)CH3], 138.3, 138.0, 137.7
(CqPh), 132.2, 130.3 (Cq-Hetar), 128.4, 128.1, 128.0, 127.7,
127.5 (CHPh), 122.4 (CH-Hetar), 120.9 (Cq-Hetar), 120.0,
117.8 (2 s, 2 × CH-Hetar), 116.0 (C-2), 109.5 (CH-Hetar),
83.1, 82.9, 79.6, 76.0, (C-1¢, C-2¢, C-3¢, C-4¢), 75.5 (CH2Ph),
75.0 (C-5¢), 74.6, 72.3 (CH2Ph), 20.9 [C(O)CH3], 18.1
(C-6¢). MS (EI, 70 eV): m/z (%) = 591 (82) [M+], 549 (20)
[benzylated indoxyl-N-rhamnoside+], 133 (16) [indoxyl+],
91 (100) [Bn+]. HRMS (EI, 70 eV): m/z calcd for C37H37NO6
[M+]: 591.26154; found: 591.26148. In addition, 10b (0.41
g, 21%) was isolated as a byproduct, Rf = 0.23 (heptane–
EtOAc = 3:1).
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