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17. (a) Demir, A. S.; Jeganathan, A. Synthesis 1992, 235–247;
(b) Melikyan, G. G. Synthesis 1993, 833–850; (c) Snider,
B. B. Chem. Rev. 1996, 96, 339–363; (d) Melikyan, G. G.
In Organic Reactions; Paquette, L. A., Ed.; Wiley: New
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Aldrichim. Acta 1998, 31, 50–64.
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1971, 3093–3096; (b) Kintsurashvili, L. G.; Vachnadze, V.
Y. Chem. Natural Compd. 2000, 36, 225–226.
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Dutschevska, H.; Kuzmanov, B. J. Serb. Chem. Soc. 1996,
61, 159–163; (b) Mukhamedova, S.; Maekh, K.; Yunusov,
S. Y. Khim. Priro Soed. 1983, 393–394.
20. General procedure: To a solution of glaucine (118 mg,
0.33 mmol) in acetic acid (5 mL) was added manga-
nese(III) acetate dihydrate (730 mg, 2.72 mmol) and the
mixture was stirred at 70 ꢁC for 2 h. After the completion
of the reaction (TLC), acetic acid was distilled off under
high vacuo, residue was dissolved in chloroform (100 mL)
and washed with saturated sodium bicarbonate solution
(50 mL) followed by water (3 · 50 mL). The organic layer
was dried over anhydrous sodium sulfate and the solvent
was distilled off under reduced pressure. The residue was
chromatographed over silica gel (10 g) using chloroform
as eluent to afford oxoglaucine 2a as yellow fine needles,
yield 88 mg (75%); mp = 196–198 ꢁC; 1H NMR (200
MHz, CDCl3) d 3.94 (s, 3H, OCH3), 4.02 (s, 6H,
2 · OCH3), 4.05 (s, 3H, OCH3), 7.11 (s, 1H, C3–H), 7.69
(d, 1H, J = 5.1 Hz, C4–H), 7.94 (s, 1H, C8–H), 8.71 (s, 1H,
C11–H), 8.81 (d, 1H, J = 5.1 Hz, C5–H). Characterization
data: compound 2b, mp = 172–174 ꢁC; 1H NMR
(200 MHz, CDCl3) d 1.44 (d, 6H, J = 6.1 Hz), 1.53 (d,
6H, J = 6.1 Hz), 4.01 (s, 6H, 2 · OCH3), 4.87 (m, 2H),
7.18 (s, 1H, C3–H), 7.79 (d, 1H, J = 5.4 Hz, C4–H), 7.96 (s,
1H, C8–H), 8.75 (s, 1H, C11–H), 8.86 (d, 1H, J = 5.3 Hz,
C5–H); 13C NMR (50 MHz, CDCl3) d 21.74 (2 · q), 21.91
(2 · q), 55.97 (q), 60.35 (q), 70.89 (d), 71.15 (d), 107.23 (d),
110.61 (d), 112.17 (d), 120.16 (s), 121.27 (s), 123.15 (d),
126.67 (s), 128.75 (s), 135.43 (s), 144.51 (d), 145.32 (s),
147.81 (s), 151.54 (s), 154.59 (s), 154.78 (s), 181.28 (s); EI-
HRMS: m/z = 407.1732 (calcd for C24H25NO5: 407.1733).
Compound 2c, mp = 182–184 ꢁC; 1H NMR (400 MHz,
CDCl3–MeOH-d4) d 3.79 (s, 3H, OCH3), 4.04 (s, 3H,
OCH3), 6.88 (dd, 1H, J = 2.4 and 8.8 Hz, C9–H), 7.47 (d,
1H, J = 9.2 Hz, C2–H), 7.73 (d, 1H, J = 4.7 Hz, C4–H),
7.77 (d, 1H, J = 9.2 Hz, C3–H), 8.29 (d, 1H, J = 8.76 Hz,
C8–H), 8.35 (d, 1H, J = 2.4 Hz, C11–H), 8.65 (d, 1H,
J = 4.2 Hz, C5–H); 13C NMR (100 MHz, CDCl3–MeOH-
d4)d 55.15 (q), 56.25 (q), 112.27 (s), 113.51 (d), 113.78 (d),
119.67 (d), 124.89 (d), 124.99 (s), 125.85 (s), 130.72 (d),
130.79 (d), 132.30 (s), 136.57 (s), 141.81 (d), 144.55 (s),
158.99 (s), 164.19 (s), 180.69 (s); EI-HRMS: m/z =
291.0903 (calcd for C18H13NO3: 291.0895). Compound
2d, mp = 180–182 ꢁC; 1H NMR (200 MHz, CDCl3) d 4.05
(s, 3H, OCH3), 4.08 (s, 3H, OCH3), 4.10 (s, 3H, OCH3),
7.24 (s, 1H, C3–H), 7.75 (d, 1H, J = 5.2 Hz, C4–H), 8.34 (s,
1H, C8–H), 8.85 (d, 1H, J = 5.2 Hz, C5–H), 8.93 (s, 1H,
C11–H); 13C NMR (50 MHz, CDCl3) d 56.35 (q), 56.47
(q), 60.88 (q), 107.54 (d), 110.28 (d), 115.54 (s), 118.39 (s),
121.97 (s), 122.58 (d), 123.67 (d), 126.65 (s), 135.37 (s),
135.95 (s), 138.80 (s), 144.76 (s), 145.12 (d), 152.41 (s),
155.55 (s), 156.53 (s), 180.12 (s); EI-HRMS: m/z =
469.0439 (calcd for C20H14F3NO7S: 469.0443). Com-
pound 2e, mp = 190–192 ꢁC; 1H NMR (400 MHz, CDCl3)
d 4.04 (s, 3H, OCH3), 4.06 (s, 3H, OCH3), 4.09 (s, 3H,
OCH3), 7.79 (s, 1H, C3–H), 7.90 (d, 1H, J = 5.3 Hz,
C4–H), 7.98 (s, 1H, C8–H), 8.63 (s, 1H, C11–H), 9.03 (d,
1H, J = 5.3 Hz, C5–H); 13C NMR (100 MHz, CDCl3) d
56.26 (q), 56.33 (q), 61.23 (q), 109.97 (d), 110.19 (d),
117.10 (s), 120.10 (d), 122.95 (s), 124.50 (d), 126.83 (s),
127.76 (s), 133.69 (s), 145.74 (d), 146.37 (s), 146.96 (s),
150.40 (s), 150.49 (s), 154.24 (s), 180.45 (s); EI-HRMS:
m/z = 469.0447 (calcd for C20H14F3NO7S: 469.0443).
21. For synthesis of atheroline: (a) Kametani, T.; Nitadori,
R.; Terasawa, H.; Takahashi, K.; Ihara, M.; Fukumoto,
K. Tetrahedron 1977, 33, 1069–1071; (b) Kametani, T.;
Nitadori, R.; Terasawa, H.; Takahashi, K.; Ihara, M.
Hetereocycles 1975, 3, 821–825; (c) Cava, M. P.; Noguchi,
I. J. Org. Chem. 1972, 37, 2936–2939; For isolation: (d)
Bick, I. R. C.; Douglas, G. K. Tetrahedron Lett. 1965,
2399–2403; (e) Chen, J. J.; Chang, Y. L.; Teng, C. M.;
Chen, I. S. Planta Med. 2001, 67, 593–598, and references
cited therein.
22. (a) Huang, W. J.; Chen, C. H.; Singh, O. V.; Lee, S. L.;
Lee, S. S. Synth. Commun. 2002, 32, 3681–3686; (b)
Carlsen, P. H. J.; Liberkova, K.; Harrex, R.; Roee, J.
Acta. Chem. Scand. 1997, 51, 343–344.
23. (a) Paquette, L. A. In Encyclopedia of Reagents for
Organic Synthesis; Wiley: New York, 1996; Vol. 3, p
4096; (b) Hendrickson, J. B.; Bergeron, R. Tetrahedron
Lett. 1973, 14, 4607–4610; (c) Hendrickson, J. B.;
Bergeron, R. Tetrahedron Lett. 1973, 14, 3839–3842; (d)
McMurry, J. E.; Scott, W. J. Tetrahedron Lett. 1983, 24,
979–982.
1
24. Characterization data of compound 8: mp = >260 ꢁC; H
NMR (200 MHz, MeOH-d4): d 4.00 (s, 3H, OCH3), 4.02
(s, 6H, 2 · OCH3), 7.19 (s, 1H, C3–H), 7.70 (d, 1H,
J = 4.78 Hz, C4–H), 7.88 (s, 1H, C8–H), 8.59 (d, 1H, J =
4.60 Hz, C5–H), 8.74 (s, 1H, C11–H).