2528
D. Böse et al.
PAPER
1-Acetoxy-8-hydroxy-9,10-dioxo-1,4,4a,9,9a,10-hexahydroan-
thracene (3A) and 1-Acetoxy-5-hydroxy-9,10-dioxo-
1,4,4a,9,9a,10-hexahydroanthracene (3B)
Regioisomer A; 1-[(tert-Butyldimethylsilyl)oxy]-8-hydroxy-
9,10-dioxo-1,4,4a,9a-tetrahydroanthracene (4A)
Mp 160 °C.
Juglone (1a; 196 mg, 1.13 mmol) was reacted with (E)-1-acetoxy-
buta-1,3-diene (2a; 401 mg, 3.58 mmol, 3.17 equiv) according to
GP A. The was reaction stopped after 2 d and the adduct 3 was iso-
lated after column chromatography (PE–EtOAc, 85:15) as a 4:1
(A:B) mixture of regioisomers (318 mg, 99%). Regioisomers 3A
and 3B were separated using MPLC (PE–EtOAc, 85:15) yielding
pure regioisomer A and a 1:3 (A:B) mixture of the two isomers as
pale yellow solids; Rf = 0.1 (PE–EtOAc, 90:10).
FT-IR (Diamond-ATR, neat): 2951, 2930, 2876, 2858, 1698, 1637,
1452, 1327, 1246, 1158, 1107, 1040, 950, 896, 824, 776, 698 cm–1.
1H NMR (600 MHz, CDCl3): δ = –0.35, –0.13 [2 s, 2 × 3 H,
Si(CH3)2], 0.44 [s, 9 H, SiC(CH3)3], 2.19 (dddd, J = 19.1, 7.0, 2.7,
2.7 Hz, 1 H, 4-Ha), 3.19 (dddd, J = 19.1, 4.7, 2.0, 0.9 Hz, 1 H, 4-Hb),
3.29–3.34 (m, 2 H, 4a-H, 9a-H), 4.45 (ddd, J = 5.0, 3.8, 1.4 Hz, 1 H,
1-H), 5.80 (dddd, J = 10.2, 5.0, 2.7, 2.0 Hz, 1 H, 2-H), 5.92 (ddd,
J = 10.2, 4.7, 2.7 Hz, 1 H, 3-H), 7.16 (dd, J = 8.4, 1.2 Hz, 1 H, 7-H),
7.48 (dd, J = 7.5, 1.2 Hz, 1 H, 5-H), 7.56 (dd, J = 8.4, 7.5 Hz, 1 H,
6-H), 12.20 (s, 1 H, 8-OH).
MS (ESI, +): m/z = 304.1 [100, (M + NH4)+], 309.0 [100, (M +
Na)+], 325.1 [30, (M + K)+].
Anal. Calcd for C16H14O5: C, 67.13; H, 4.93. Found: C, 66.94 ±
0.10; H, 4.92 ± 0.01.
13C NMR (151 MHz, CDCl3): δ = –5.7, –4.9 [Si(CH3)2], 17.5 (SiC),
21.8 (C-4), 25.1 [SiC(CH3)3], 42.4 (C-4a), 53.3 (C-9a), 65.5 (C-1),
117.3 (C-5), 119.4 (C-8a), 122.4 (C-7), 126.9 (C-2), 128.8 (C-3),
136.4 (C-6), 137.8 (C-10a), 161.6 (C-8), 195.2 (C-10), 205.5 (C-9).
Regioisomer A; 1-Acetoxy-8-hydroxy-9,10-dioxo-
1,4,4a,9,9a,10-hexahydroanthracene (3A)
Mp 132 °C.
Regioisomer B; 1-[(tert-Butyldimethylsilyl)oxy]-5-hydroxy-
9,10-dioxo-1,4,4a,9a-tetrahydroanthracene (4B)
Mp 138 °C.
FT-IR (Diamond-ATR, neat): 3040, 1740, 1702, 1642, 1454, 1369,
1246, 1221, 1162, 1017, 824, 714 cm–1.
1H NMR (600 MHz, CDCl3): δ = 1.38 (s, 3 H, COCH3), 2.24 (dddd,
J = 19.2, 7.1, 2.7, 2.3 Hz, 1 H, 4-Ha), 3.25 (ddd, J = 19.2, 4.8,
2.0 Hz, 1 H, 4-Hb), 3.42 (dd, J = 7.1, 6.0 Hz, 1 H, 4a-H), 3.47 (dd,
J = 6.0, 4.0 Hz, 1 H, 9a-H), 5.47 (dd, J = 5.1, 4.0 Hz, 1 H, 1-H), 5.93
(dddd, J = 10.1, 5.1, 2.3, 2.0 Hz, 1 H, 2-H), 6.09 (ddd, J = 10.1, 4.8,
2.7 Hz, 1 H, 3-H), 7.23 (dd, J = 8.4, 1.2 Hz, 1 H, 7-H), 7.56 (dd, J =
7.5, 1.2 Hz, 1 H, 5-H), 7.64 (dd, J = 8.4, 7.5 Hz, 1 H, 6-H), 11.99 (s,
1 H, 8-OH).
13C NMR (151 MHz, CDCl3): δ = 20.0 (COCH3), 21.9 (C-4), 42.4
(C-4a), 50.7 (C-9a), 65.8 (C-1), 117.3 (C-5), 118.4 (C-8a), 122.8
(C-2), 123.0 (C-7), 131.8 (C-3), 136.8 (C-10a), 136.9 (C-6), 161.7
(C-8), 169.2 (C=O), 194.8 (C-10), 203.0 (C-9).
FT-IR (Diamond-ATR, neat): 2955, 2883, 2929, 2857, 1690, 1651,
1455, 1331, 1298, 1263, 11207, 1161, 1046, 953, 894, 836, 777,
716 cm–1.
1H NMR (600 MHz, CDCl3): δ = –0.39, –0,13 [2 s, 2 × 3 H,
Si(CH3)2], 0.46 [s, 9 H, SiC(CH3)3], 2.16 (dddd, J = 19.2, 7.5, 2.6,
2.6 Hz, 1 H, 4-Ha), 3.23 (ddd, J = 19.2, 4.7, 1.2 Hz, 1 H, 4-Hb), 3.28
(dd, J = 6.0, 3.8 Hz, 1 H, 9a-H), 3.42 (dd, J = 7.5, 6.0 Hz, 1 H, 4a-
H), 4.45 (ddd, J = 4.8, 3.8, 1.2 Hz, 1 H, 1-H), 5.82 (ddd, J = 10.2,
4.8, 2.7 Hz, 1 H, 2-H), 5.90 (dddd, J = 10.2, 4.7, 2.6, 1.2 Hz, 1 H, 3-
H), 7.19 (dd, J = 8.3, 1.2 Hz, 1 H, 6-H), 7.54 (dd, J = 8.3, 7.6 Hz,
1 H, 7-H), 7.61 (dd, J = 7.6, 1.2 Hz, 1 H, 8-H), 11.64 (s, 1 H, 5-OH).
13C NMR (151 MHz, CDCl3): δ = –5.6, –4.9 [Si(CH3)2], 17.5 (SiC),
21.2 (C-4), 25.1 [SiC(CH3)3], 42.0 (C-4a), 52.8 (C-9a), 65.5 (C-1),
118.0 (C-8), 119.9 (C-10a), 123.4 (C-6), 127.5 (C-2), 128.3 (C-3),
135.2 (C-7), 136.2 (C-8a), 159.9 (C-5), 197.7 (C-9), 202.8 (C-10).
Regioisomer 3B; 1-Acetoxy-5-hydroxy-9,10-dioxo-
1,4,4a,9,9a,10-hexahydroanthracene (3B)
Mp 120 °C.
FT-IR (Diamond-ATR, neat): 3041, 1740, 1695, 1650, 1455, 1369,
1-Acetoxy-3-methyl-8-hydroxy-9,10-dioxo-1,4,4a,9,9a,10-hexa-
hydroanthracene (5A) and Acetoxy-3-methyl-5-hydroxy-9,10-
dioxo-1,4,4a,9,9a,10-hexahydroanthracene (5B)
1266, 1224, 1163, 1016, 824, 716 cm–1.
1H NMR (600 MHz, CDCl3): δ = 1.39 (s, 3 H, COCH3), 2.20–2.29
(m, 1 H, 4-Ha), 3.20–3.30 (m, 1 H, 4-Hb), 3.40–3.53 (m, 2 H, 9a-H,
4a-H), 5.47 (dd, J = 4.9, 4.0 Hz, 1 H, 1-H), 5.93 (dddd, J = 10.2, 4.9,
2.3, 2.3 Hz, 1 H, 2-H), 6.08 (ddd, J = 10.2, 4.8, 2.7 Hz, 1 H, 3-H),
7.26 (dd, J = 8.1, 1.5 Hz, 1 H, 6-H), 7.58 (dd, J = 7.4, 1.5 Hz, 1 H,
8-H), 7.61 (dd, J = 8.1, 7.4 Hz, 1 H, 7-H), 11.75 (s, 1 H, 5-OH).
13C NMR (151 MHz, CDCl3): δ = 20.0 (COCH3), 21.6 (C-4), 42.3
(C-4a), 50.3 (C-9a), 65.7 (C-1), 118.2 (C-8), 118.8 (C-10a), 123.5
(C-2), 123.8 (C-6), 131.1 (C-3), 135.7 (C-8a), 136.0 (C-7), 160.2
(C-5), 169.1 (C=O), 195.4 (C-9), 202.3 (C-10).
Juglone (1a; 155 mg, 0.89 mmol) was reacted with (E)-1-acetoxy-
3-methylbuta-1,3-diene (2c; 336 mg, 2.66 mmol, 2.99 equiv) ac-
cording to GP A. The reaction was stopped after 18 h and the adduct
5 was isolated after column chromatography (PE–EtOAc, 85:15) as
a 4.4:1 (A:B) mixture of regioisomers (259 mg, 97%). Regioiso-
mers 5A and 5B were separated using MPLC (PE–EtOAc, 85:15)
yielding pure regioisomer A and a 1:2.3 (A:B) mixture of the two
isomers as pale yellow solids; Rf = 0.1 (PE–EtOAc, 90:10).
Regioisomer A; 1-Acetoxy-3-methyl-8-hydroxy-9,10-dioxo-
1,4,4a,9,9a,10-hexahydroanthracene (5A)
Mp 141 °C.
1-[(tert-Butyldimethylsilyl)oxy]-8-hydroxy-9,10-dioxo-
1,4,4a,9a-tetrahydroanthracene (4A) and 1-[(tert-Butyldimeth-
ylsilyl)oxy]-5-hydroxy-9,10-dioxo-1,4,4a,9a-tetrahydroanthra-
cene (4B)
FT-IR (Diamond-ATR, neat): 2916, 1739, 1702, 1642, 1454, 1368,
1346, 1240, 1219, 1159, 1014, 925, 901, 826, 770, 729 cm–1.
1H NMR (600 MHz, CDCl3): δ = 1.36 (s, 3 H, COCH3), 1.84 (s,
3 H, 3-CH3), 2.15 (ddd, J = 18.7, 7.3, 3.0 Hz, 1 H, 4-Ha), 3.12 (d,
J = 18.7 Hz, 1 H, 4-Hb), 3.38 (dd, J = 6.0, 4.0 Hz, 1 H, 9a-H), 3.43
(dd, J = 7.3, 6.0 Hz, 1 H, 4a-H), 5.45 (dd, J = 5.5, 4.0 Hz, 1 H, 1-H),
5.67 (dd, J = 5.5, 3.0 Hz, 1 H, 2-H), 7.22 (dd, J = 8.4, 1.2 Hz, 1 H,
7-H), 7.55 (dd, J = 7.6, 1.2 Hz, 1 H, 5-H), 7.63 (dd, J = 8.4, 7.6 Hz,
1 H, 6-H), 12.00 (s, 1 H, 8-OH).
13C NMR (151 MHz, CDCl3): δ = 20.0 (COCH3), 23.5 (3-CH3),
26.9 (C-4), 43.1 (C-4a), 50.5 (C-9a), 67.0 (C-1), 117.2 (C-5), 117.7
(C-2), 118.4 (C-8a), 123.0 (C-7), 136.8 (C-6), 136.8 (C-10a), 140.5
(C-3), 161.6 (C-8), 169.3 (C=O), 194.9 (C-10), 203.3 (C-9).
Juglone (1a; 299 mg, 1.15 mmol) was reacted with (E)-1-(tert-bu-
tyldimethylsilyl)oxybuta-1,3-diene (2d; 635 mg, 3.45 mmol,
3.00 equiv) according to GP A. The reaction was stopped after 21 h
and the adducts 4A and 4B were isolated after column chromatog-
raphy (PE–EtOAc, 90:10) as a 7:1 (A:B) mixture of regioisomers
(250 mg, 61%). Regioisomers 4A and 4B were separated using
MPLC (PE–EtOAc, 90:10) yielding pure regioisomers A and B as
pale yellow solids; Rf = 0.3 (PE–EtOAc, 90:10).
MS (ESI, +): m/z (%) = 381.2 [100, (M + NH4)+], 358.8 [40, (M +
H)+].
Anal. Calcd for C20H26O4Si: C, 67.00; H, 7.31. Found: C, 66.96 ±
<0.1; H, 7.39 ± 0.02.
MS (ESI, +): m/z (%) = 317.9 [100, (M + NH4)+], 323.2 [90, (M +
Na)+].
Synthesis 2014, 46, 2524–2532
© Georg Thieme Verlag Stuttgart · New York