Y. Luo et al. / Tetrahedron 62 (2006) 2465–2470
2469
(m, 2H), 2.22 (s, 3H), 2.41 (s, 3H), 5.36 (s, 2H), 5.40 (d, JZ
References and notes
17.4 Hz, 1H), 5.68 (d, JZ17.4 Hz, 1H), 7.17 (s, 1H), 7.43–
7.49 (m, 3H), 7.60 (dd, JZ9.0, 2.4 Hz, 1H), 7.69–7.72 (m,
2H), 8.13 (d, JZ2.4 Hz, 1H), 8.21 (d, JZ9.0 Hz, 1H). 13C
NMR (100 MHz, CDCl3): dZ7.5, 20.6, 21.2, 31.7, 50.2,
66.9, 75.8, 81.4, 96.1, 104.9, 116.8, 120.5, 121.0, 125.3,
126.2, 128.0, 128.7, 130.2, 130.8, 131.3, 132.1, 145.8,
146.1, 146.7, 150.2, 151.5, 157.1, 167.4, 169.1, 169.8. MS
(EI): m/zZ548, 418 (base peak). HRMS (EI): m/z calcd for
C32H24N2O7 [MC]: 548.1584; found: 548.1597.
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4.1.7. 10-Acetoxyl-20-acetyl-7-(2-trimethylsilylethynly)-
camptothecin (13c). To a mixture of 7-chloride 12 (97 mg,
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0.2 mmol),
Pd(OAc)2
(0.04 mmol),
rac-BINAP
(0.08 mmol) and potassium carbonate (0.4 mmol), under
an argon atmosphere, was added a solution of trimethylsi-
lylacetylene (0.8 mmol) in degassed toluene (17 mL). The
reaction mixture was heated at 100 8C for 9 h in sealed tube.
Then the solvent was evaporated to give a residue, which
was purified by flash column chromatography (acetone/
chloroform, 1:20) to give 65 mg of pure 13c (60% yield). 1H
NMR (300 MHz, CDCl3): dZ0.38 (s, 9H), 0.97 (t, JZ
6.9 Hz, 3H), 2.10–2.31 (m, 2H), 2.20 (s, 3H), 2.42 (s, 3H),
5.30 (s, 2H), 5.40 (d, JZ18 Hz, 1H), 5.68 (d, JZ18 Hz,
1H), 7.17 (s, 1H), 7.60 (dd, JZ9.3, 2.7 Hz, 1H), 8.05 (d, JZ
2.4 Hz, 1H), 8.20 (d, JZ9.0 Hz, 1H). 13C NMR (100 MHz,
CDCl3): dZK0.3, 7.5, 20.7, 21.2, 31.7, 50.2, 67.0, 75.8,
96.1, 96.3, 112.4, 116.9, 120.6, 125.1, 126.2, 128.2, 131.3,
131.4, 145.8, 146.1, 146.7, 150.2, 151.6, 157.2, 167.4,
169.1, 169.8. MS (EI): m/zZ544, 414 (base peak). HRMS
(EI): m/z calcd for C29H28SiN2O7 [MC]: 544.1666; found:
544.1670.
5. Miyasaka, T.; Sawada, S.; Nokata, K.; Sugino, E.; Mutai, M.
U.S. Patent 4,604,463.
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Pinedo, H. M. Ann. N.Y. Acad. Sci. 2000, 922, 175–177.
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Strode, J. T.; Kohlhagen, G.; Du, W.; Chavan, A. J.; Fraley,
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Gallo, G.; Marzi, M.; Tinti, M. O.; Martinelli, R.; Pisano, C.;
Carminati, P.; Carenini, N.; Beretta, G.; Perego, P.; Cesare,
M. D.; Pratesi, G.; Zunino, F. J. Med. Chem. 2001, 44,
3264–3274.
9. Fan, Y.; Weinstein, J. N.; Kohn, K. W.; Shi, L. M.; Pommier,
Y. J. Med. Chem. 1998, 41, 2216–2226.
10. Dallavalle, S.; Merlini, L.; Penco, S.; Zunino, F. Expert. Opin.
Ther. Patents 2002, 12, 837–844.
11. (a) Sawada, S.; Okajima, S.; Aiyama, R.; Nokata, K.; Furuta,
T.; Yokokura, T.; Sugino, E.; Yamaguchi, K.; Miyasaka, T.
Chem. Pharm. Bull. 1991, 39, 1446–1454. (b) Sawada, S.;
Matsuoka, S.; Nokata, K.; Nagata, H.; Furuta, T.; Yokokura,
T.; Miyasaka, T. Chem. Pharm. Bull. 1991, 39, 3183–3188. (c)
Sawada, S.; Nokata, K.; Furuta, T.; Yokokura, T.; Miyasaki, T.
Chem. Pharm. Bull. 1991, 39, 2574–2580.
4.1.8. BNP-1350 (3). 1H NMR (300 MHz, CDCl3): dZ0.17
(s, 9H), 0.87–0.94 (m, 2H), 1.03 (t, JZ7.2 Hz, 3H),
1.84–1.92 (m, 2H), 3.06–3.11 (m, 2H), 5.22 (s, 2H), 5.30
(d, JZ16.8 Hz, 1H), 5.75 (d, JZ16.8 Hz, 1H), 7.62–7.67
(m, 2H), 7.79 (dd, JZ7.2, 7.8 Hz, 1H), 8.02 (d, JZ8.4 Hz,
1H), 8.22 (d, JZ8.4 Hz, 1H). 13C NMR (100 MHz, CDCl3):
dZK1.8, 7.8, 17.7, 24.1, 31.5, 49.2, 66.3, 72.7, 98.0, 118.4,
123.2, 126.0, 126.6, 127.6, 129.9, 130.7, 147.0, 149.4,
150.1, 151.9, 157.6, 173.9. MS (EI): m/zZ448, 448 (base
peak). HRMS (EI): m/z calcd for C25H28SiN2O4 [MC]:
448.1818; found: 448.1814.
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28, 489–519. (b) Du, W. Tetrahedron 2003, 59, 8649–8687.
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4.1.9. SN-38 (2). 1H NMR (300 MHz, DMSO-d6): dZ0.85
(t, JZ7.5 Hz, 3H), 1.28 (t, JZ7.5 Hz, 3H), 1.80–1.88 (m,
2H), 3.06 (q, JZ7.5 Hz, 2H), 5.25 (s, 2H), 5.39 (s, 2H), 7.23
(s, 1H), 7.38 (s, 1H), 7.40 (d, JZ9.9 Hz, 1H), 8.01 (d, JZ
9.9 Hz, 1H). 13C NMR (100 MHz, DMSO-d6): dZ7.8, 13.4,
22.3, 30.2, 49.4, 65.3, 72.4, 95.9, 104.7, 118.1, 122.3, 127.9,
128.2, 131.6, 142.8, 143.6, 146.4, 148.8, 150.1, 156.5,
156.9, 172.6. MS (EI): m/zZ392, 348 (base peak). HRMS
(EI): m/z calcd for C22H20N2O5 [MC]: 392.1372; found:
392.1383.
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Acknowledgements
We gratefully acknowledge the financial support from
Shanghai Science and Technology Mission (Grant
044319216).