ORDER
REPRINTS
Syntheses of Idarubicinone-7-b-D-glucuronide
1715
(lit.[15a] 173–175, lit.[17a] 176–1788C); 1H NMR (DMSO-d6) d 13.25 (s, 1H,
OH), 13.10 (s, 1H, OH), 8.13–8.09 (m, 2H, ArH), 7.90–7.88 (m, 2H, ArH),
6.06 (s, 1H, C7eqH), 5.26 (s, 1H, C7OH), 4.91 (s, 1H, C9OH), 2.93 (d, 1H,
J ¼ 18.6 Hz, C10H), 2.77 (d, 1H, J ¼ 18.0 Hz, C10H), 2.31 (s, 3H, COCH3),
2.16 (d, 1H, J ¼ 13.7 Hz, C8H), 1.90 (dd, 1H, J ¼ 14.2, 4.39 Hz, C8H); 13C
NMR (DMSO-d6) d 211.85, 186.06, 185.83, 156.16, 155.38, 136.85,
135.15, 134.96, 134.86, 132.70, 132.52, 126.47, 126.44, 110.36, 109.82,
76.24, 60.43, 35.71, 32.11, 24.45; MS (FABþ, Na) m/z 391.0 (M þ Na)þ.
3-Acetyl-3,5,12-trihydroxy-6,11-dioxo-1,2,3,4,6,11-hexahydro-1-naph-
thacenyl (2R)-2-(acetyloxy)-2-phenylethanoate (17). (+)-Idarubicinone
3b (0.15 g, 0.41 mmol) and (S)-(þ)-O-acetylmandelic acid (0.30 g,
1.54 mmol) in the presence of dicyclohexylcarbodiimide (DCC, 0.30 g,
1.45 mmol) and 4-(dimethylamino) pyridine (DMAP) (0.03 g, 0.24 mmol)
in anhydrous dichloromethane were stirred at r.t. for 15 hr. After filtration
of the precipitated urea, solvent was removed under reduced pressure and
the residue was purified by column chromatography with acetone/dichloro-
methane (1 : 20) as eluent. Two products are obtained 17a (0.11 g, 47%) and
17b (0.09 g, 40%) as red crystals: 17a; m.p. 98–1008C; [a]2D0 þ77.78 (c 0.1,
dichloromethane); IR (KBr) 2942, 2840, 1745, 1631, 1591, 1427, 1381,
1
1176, 1046, 983, 792, 741, 695 cm21; H NMR (CDCl3) d 13.31 (s, 1H,
ArOH), 12.99 (s, 1H, ArOH), 8.35–8.31 (m, 2H, ArH), 7.83–7.86 (m,
2H, ArH), 7.48–7.51 (m, 2H, ArH), 7.39–7.36 (m, 3H, ArH), 6.36 (d, 1H,
J ¼ 3.9 Hz, OCOCH), 5.72 (s, 1H, C7eqH), 3.32 (dd, 1H, J ¼ 2.0, 18.6 Hz,
C10H), 2.95 (d, 1H, J ¼ 19.0 Hz, C10H), 2.46 (s, 3H, OCH3), 2.27 (d, 1H,
J ¼ 5.9 Hz, C8H), 2.24 (s, 3H, OCH3), 2.2–2.17 (m, 2H); 13C NMR
(CDCl3) d 212.29, 187.04, 186.40, 171.56, 168.09, 156.37, 155.98, 137.23,
134.61, 134.48, 133.47, 133.33, 132.36, 130.39, 129.39, 128.67, 127.34,
127.11, 126.97, 111.97, 110.62, 75.75, 75.59, 64.29, 33.74, 32.19, 30.92,
24.76, 20.73; UV lmax (log 1) 252 (0.94), 258 (0.90), 283 (0.27), 487
(0.23). 17b; m.p. 82–848C; [a]2D0 þ40.18 (c 0.1, CH2Cl2); IR (KBr) 2933,
1748, 1630, 1594, 1428, 1374, 1238, 1053, 982, 926, 789, 738, 685 cm21
;
1H NMR (CDCl3) d 13.28 (s, 1H, ArOH), 13.27 (s, 1H, ArOH), 8.35–8.33
(m, 2H, ArH), 7.87–7.82 (m, 2H, ArH), 7.50–7.47 (m, 2H, ArH), 7.44–
7.37 (m, 3H, ArH), 6.51 (d, 1H, J ¼ 4.4 Hz, OCOCH), 5.96 (s, 1H,
C
7eqH), 3.20 (dd, 1H, J ¼ 2.0, 18.8 Hz, C10H), 2.85 (d, 1H, J ¼ 19.0 Hz,
C10H), 2.61 (s, 1H, C9OH), 2.27 (s, 3H, OCH3), 2.24–2.22 (m, 2H, CH2),
2.20 (s, 3H, COCH3), 2.18–2.17 (m, 2H, CH2), 2.06–2.02 (m, 1H, CH2);
13C NMR (CDCl3) d 211.43, 187.07. 186.46, 170.98, 167.22, 156.38,
155.82, 136.90, 134.68, 134.50, 133.47, 133.44, 133.26, 130.33, 129.59,
128.98, 127.89, 127.08, 127.06, 112.03, 110.74, 75.37, 74.83, 63.63,
34.38, 32.25, 30.92, 24.46, 20.80; UV lmax (log 1) 253 (1.09), 258 (1.09),
487 (0.26).