910
H. Wu et al.
LETTER
(10) Analytical Data
Acknowledgment
Compound 21a: 1H NMR (400 MHz, CDCl3): d = 0.32 (br,
1 H), 1.60–1.64 (m, 1 H), 1.74 (d, J = 7.6 Hz, 3 H), 2.04–
2.12 (m, 1 H), 2.64–2.72 (m, 1 H), 2.69 (s, 3 H), 3.18–3.33
(m, 2 H), 3.72–3.79 (m, 1 H), 3.94 (s, 3 H), 4.25–4.29 (m, 1
H), 4.74–4.81 (m, 2 H), 5.16 (br, 1 H), 5.40 (s, 1 H), 5.62–
5.67 (m, 2 H), 6.50 (t, J = 6.8 Hz, 1 H), 6.61 (t, J = 8.0 Hz, 1
H), 6.71 (d, J = 6.8 Hz, 1 H), 6.92 (t, J = 7.6 Hz, 2 H), 7.17
(t, J = 7.6 Hz, 2 H), 7.31–7.34 (m, 1 H), 7.39–7.43 (m, 2 H),
7.53–7.56 (m, 5 H), 7.65–7.74 (m, 4 H). 13C NMR (100
MHz, CDCl3): d = 21.74, 29.32, 29.33, 30.55, 34.19, 34.20,
36.04, 52.09, 52.10, 54.70, 69.23, 72.65, 92.73, 99.60,
99.73, 112.95, 113.43, 121.13, 122.66, 122.67, 123.75,
124.77, 126.83, 127.48, 127.50, 127.51 127.78, 127.79,
127.85, 128.11, 128.17, 128.43, 128.44, 128.45, 128.46,
129.50, 130.86, 132.19, 133.42, 133.48, 137.03, 144.82,
151.73, 153.36, 154.89, 167.61. HRMS: m/z [M + H+] calcd
for C46H43N4O6: 747.3183; found: 747.3142. IR (KBr):
3463, 2950, 2875, 1712, 1608, 1446, 1393, 1208, 716 cm–1.
[a]D20 +1.98 (c 1.0, CHC13).
This work was supported by grants from NSFC (20825207,
21021001), PCSIRT (IRT0846), the National Basic Research Pro-
gram of China (973 program, 2010CB833200), the National S & T
Major Project of China (2009ZX09310-002), and the State Key La-
boratory of Bioorganic and Natural Products Chemistry, Shanghai
Institute of Organic Chemistry.
References and Notes
(1) Numata, A.; Takahashi, C.; Ito, Y.; Takada, T.; Kawai, K.;
Usami, Y.; Matsumura, E.; Imachi, M.; Ito, T.; Hasegawa, T.
Tetrahedron Lett. 1993, 34, 2355.
(2) (a) Dalsgaard, P. W.; Blunt, J. W.; Munro, M. H. G.; Frisvad,
J. C.; Christophersen, C. J. Nat. Prod. 2005, 68, 258.
(b) Jadulco, R.; Edrada, R. A.; Ebel, R.; Berg, A.;
Schaumann, K.; Wray, V.; Steube, K.; Proksch, P. J. Nat.
Prod. 2004, 67, 78. (c) Hayashi, H.; Matsumoto, H.;
Akiyama, K. Biosci. Biotechnol. Biochem. 2004, 68, 753.
(3) Verbitski, S. M.; Mayne, C. L.; Davis, R. A.; Concepcion,
G. P.; Ireland, C. M. J. Org. Chem. 2002, 67, 7124.
(4) (a) Evans, M. A.; Sacher, J. R.; Weinreb, S. M. Tetrahedron
2009, 65, 6712. (b) George, J. H.; Adlington, R. M. Synlett
2008, 2093. (c) Siengalewicz, P.; Gaich, T.; Mulzer, J.
Angew. Chem. Int. Ed. 2008, 47, 8170. (d) Crawley, S.;
Funk, R. L. Org. Lett. 2006, 8, 3995. (e) Seo, J. H.; Artman,
G. D.; Weinreb, S. M. J. Org. Chem. 2006, 71, 8891.
(f) Yang, J.; Song, H.; Xiao, X.; Wang, J.; Qin, Y. Org. Lett.
2006, 8, 2187. (g) May, J. A.; Stoltz, B. M. Tetrahedron
2006, 62, 5262; and references cited therein. (h) Crawley,
S.; Funk, R. L. Org. Lett. 2003, 5, 3169. (i) Artman, G. D.;
Weinreb, S. M. Org. Lett. 2003, 5, 1523. (j) May, J. A.;
Zeidan, R. K.; Stoltz, B. M. Tetrahedron Lett. 2003, 44,
1203.
(5) (a) Fuchs, J. R.; Funk, R. L. J. Am. Chem. Chem. 2004, 126,
5068. (b) Sabahi, A.; Novikov, A.; Rainier, J. D. Angew.
Chem. Int. Ed. 2006, 45, 4317.
(6) (a) Yang, J.; Wu, H. X.; Shen, L. Q.; Qin, Y. J. Am. Chem.
Soc. 2007, 129, 13794. (b) Liu, P.; Seo, J. H.; Weinreb,
S. M. Angew. Chem. Int. Ed. 2010, 49, 2000. (c) Seo, J. H.;
Liu, P.; Weinreb, S. M. J. Org. Chem. 2010, 75, 2667.
(7) Zuo, Zh. W.; Xie, W. Q.; Ma, D. W. J. Am. Chem. Soc. 2010,
132, 13226.
Compound 21b: 1H NMR (400 MHz, CDCl3): d = 1.57 (s, 3
H), 1.71 (d, J = 6.8 Hz, 3 H), 1.80–1.84 (m, 1 H), 2.05–2.12
(m, 1 H), 2.60–2.68 (m, 1 H), 2.87–2.94 (m, 1 H), 3.48–3.55
(m, 1 H), 3.73–3.79 (m, 1 H), 3.80–3.96 (m, 1 H), 3.96 (s, 3
H), 4.31–4.35 (m, 1 H), 5.15 (d, J = 11.6 Hz, 1 H), 5.29 (d,
J = 11.6 Hz, 1 H), 5.30–5.36 (m, 2 H), 5.32 (br, 1 H), 5.49
(d, J = 7.6 Hz, 1 H), 6.07 (d, J = 8.4 Hz, 1 H), 6.55–6.57 (m,
1 H), 6.75 (t, J = 8.0 Hz, 1 H), 6.89–6.93 (m, 1 H), 6.93–6.97
(m, 1 H), 7.24–7.28 (m, 1 H), 7.33–7.43 (m, 6 H), 7.65–7.67
(m, 2 H), 7.72–7.74 (m, 2 H), 7.75–7.78 (m, 2 H), 7.85–7.89
(m, 2 H). 13C NMR (100 MHz, CDCl3): d = 20.05, 29.42,
29.66, 31.15, 35.40, 36.97, 52.39, 53.18, 54.40, 69.79,
72.49, 72.92, 93.04, 99.56, 100.00, 113.03, 113.25, 121.26,
123.13, 123.14, 124.53, 125.04, 127.08, 127.10, 127.71,
127.72, 127.86, 127.88, 128.12, 128.15, 128.35, 128.47,
129.14, 129.15, 129.88, 131.15, 132.27, 133.80, 133.82,
137.68, 141.41, 144.51, 151.69, 153.57, 155.46, 168.06.
HRMS: m/z [M + H+] calcd for C46H43N4O6: 747.3183;
found: 747.3141. IR (KBr): 3464, 2951, 2868, 1709, 1606,
1445, 1389, 1189, 719 cm–1. [a]D20 –0.43 (c 1.0, CHC13).
(11) The crystallographic data of 21a (C46H42N4O6) have been
deposited with the Cambridge Crystallographic Data Centre;
the entry CCDC 776462 contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from the Cambridge Crystallo-
cif.
(8) Wu, H. X.; Xue, F.; Xiao, X.; Qin, Y. J. Am. Chem. Soc.
2010, 132, 14052.
(9) Somei, M.; Yamada, F.; Kunimoto, M.; Kaneko, C.
Heterocycles 1984, 22, 797.
Synlett 2011, No. 7, 907–910 © Thieme Stuttgart · New York