3600
Y. Nishii et al. / Tetrahedron Letters 50 (2009) 3597–3601
CO2Me
CO2Me
OAc
Me
OH
Me
OCOPh
OH
O
O
MeO
O
MeO
O
H
H
Me
Me
Me
Me
N
Me
Me
N
MeOLi
OMe
OMe
O
O
O
O
O
O
MeOH, rt
45%
OCOPh
MeO
O
25
2
p-TsCl, DMAP
CH2Cl2, 0 °C ~ rt;
Me
Me
OH
O
then 23, rt
CO2Me
OAc
Me
24
OCOPh
O
MeO
O
H
N
Me
Me
Me
OMe
O
O
O
26
Scheme 4.
63, 2111; (e) Takahashi, S.; Okada, A.; Nishiwaki, M.; Nakata, T. Heterocycles
2006, 69, 487.
12. Roush, W. R.; Pfeifer, L. A. Org. Lett. 2000, 2, 859.
13. Trost, B. M.; Yang, H.; Probst, G. D. J. Am. Chem. Soc. 2004, 126, 48.
14. Sohn, J.-H.; Waizumi, N.; Zhong, H. M.; Rawal, V. H. J. Am. Chem. Soc. 2005, 127,
7290.
15. (a) Kagawa, N.; Ihara, M.; Toyota, M. Org. Lett. 2006, 8, 875; (b) Kagawa, N.;
Ihara, M.; Toyota, M. J. Org. Chem. 2006, 71, 6796.
sized via SmI2-promoted intramolecular Reformatsky-type reac-
tion, insertion of the side chain and functionalization, and con-
struction of the 4-amino-1,3-dioxadecaline ring.
Acknowledgment
16. (a) Kocienski, P. J.; Narquizian, R.; Raubo, P.; Smith, C.; Boyle, F. T. Synlett 1998,
869; See also, Ref. 18b. Synthesis of 18-O-methyl mycalamide B: (b) Kocienski,
P. J.; Raubo, P.; Davis, J. K.; Boyle, F. T.; Davies, D. E.; Richter, A. J. Chem. Soc.,
Perkin Trans. 1 1996, 1797; (c) Kocienski, P. J.; Paubo, P.; Smith, C.; Boyle, F. T.
Synthesis 1999, 2087.
17. Hong, C. Y.; Kishi, Y. J. Am. Chem. Soc. 1991, 113, 9693.
18. (a) Kocienski, P. J.; Narquizian, R.; Raubo, P.; Smith, C.; Boyle, F. T. Synlett 1998,
1432; (b) Kocienski, P.; Narquizian, R.; Raubo, P.; Smith, C.; Farrugia, L. J.; Muir,
K.; Boyle, F. T. J. chem. Soc., Perkin Trans. 2000, 1, 2357.
19. Green, M. E.; Rech, J. C.; Floreancig, P. E. Angew. Chem., Int. Ed. 2008, 47, 7317.
20. Trotter, N. S.; Takahashi, T.; Nakata, T. Org. Lett. 1999, 1, 957.
21. (a) Molander, G. A.; Etter, J. B. J. Chem. Soc. 1987, 109, 6556; (b) Molander, G. A.;
Harris, C. R. Chem. Rev. 1996, 96, 307.
We thank Professor Shigeki Matsunaga (Tokyo University) for
providing the NMR spectrum of natural theopederin B.
References and notes
1. (a) Perry, N. B.; Blunt, J. W.; Munro, M. H. G.; Pannell, L. K. J. Am. Chem. Soc.
1988, 110, 4850; (b) Perry, N. B.; Blunt, J. W.; Munro, M. H. G.; Thompson, A. M.
J. Org. Chem. 1990, 55, 223.
2. (a) Sakemi, S.; Ichiba, T.; Kohmoto, S.; Saucy, G.; Higa, T. J. Am. Chem. Soc. 1988,
110, 4851; (b) Matsunaga, S.; Fusetani, N.; Nakao, Y. Tetrahedron 1992, 48,
8369; (c) Kobayashi, J. I. F.; Shigemori, H.; Sasaki, T. J. Nat. Prod. 1993, 56, 976.
3. Theopederins A–E: (a) Fusetani, N.; Sugawara, T.; Matsunaga, S. J. Org. Chem.
1992, 57, 3828; Theopederins F–J: (b) Tsukamoto, S.; Matsunaga, S.; Fusetani,
N.; Toh-E, A. Tetrahedron 1999, 55, 13697; Theopederins K and L: (c) Paul, G. K.;
Gunasekara, S. P.; Longley, R. E.; Pomponi, S. A. J. Nat. Prod. 2002, 65, 59.
4. (a) Cardani, C.; Ghiringhelli, D.; Mondelli, R.; Quilico, A. Tetrahedron Lett. 1965,
2537; (b) Matsumoto, T.; Yanagiya, M.; Maeno, S.; Yasuda, S. Tetrahedron Lett.
1968, 6297; (c) Furusaki, A.; Watanabe, T.; Matsumoto, T.; Yanagiya, M.
Tetrahedron Lett. 1968, 6301.
5. (a) Tsuzuki, K.; Watanabe, T.; Yanagiya, M.; Matsumoto, T. Tetrahedron Lett.
1976, 4745; (b) Yanagiya, M.; Matsuda, K.; Hasegawa, K.; Matsumoto, T.
Tetrahedron Lett. 1982, 23, 4039; (c) Matsumoto, T.; Matsuda, F.; Hasegawa, K.;
Yanagiya, M. Tetrahedron 1984, 40, 2337; (d) Matsuda, F.; Tomiyoshi, N.;
Yanagiya, M.; Matsumoto, T. Tetrahedron 1988, 44, 7063.
22. Foster, A. B.; Haines, A. H.; Homer, J.; Lehmann, J.; Thomas, L. F. J. Chem. Soc.
1961, 5005.
23. Data for 9: mp 195–197 °C; ½a D23
ꢁ
+3.8 (c 1.06, CHCl3); IR (KBr) 3363, 2995, 2885,
1699, 1398, 1214, 1110, 1056, 1003 cmꢀ1
;
1H NMR (CDCl3, 500 MHz) d 7.46–
7.44 (m, 2H), 7.38–7.36 (m, 3H), 5.54 (s, 1H), 4.58 (m, 1H), 4.45 (dd, J = 13.1,
1.2 Hz, 1H), 4.26 (dd, J = 3.4, 1.8 Hz, 1H), 4.09 (dd, J = 13.1, 1.8 Hz, 1H), 3.89 (d,
J = 3.4 Hz, 1H), 1.46 (s, 3H), 1.36 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 176.6,
137.2, 129.2, 128.3, 126.1, 101.3, 74.7, 73.4, 69.9, 69.5, 41.8, 27.0, 23.0; HRMS
(FAB) calcd for C15H18O5Na (M+Na+) 301.1046, found 301.1043.
24. The procedure using t-BuOK is suitable for a large-scale preparation of 10.
25. Lewis, M. D.; Cha, J. K.; Kishi, Y. J. Am. Chem. Soc. 1982, 104, 4976.
26. Data for 12: mp 114–115 °C; ½a D24
ꢁ
+6.7 (c 1.00, CHCl3); IR (KBr) 2909, 1640,
1456, 1404, 1346, 1224, 1139, 1095, 1005 cmꢀ1
;
1H NMR (CDCl3, 400 MHz) d
6. (a) Nakata, T.; Nagao, S.; Mori, N.; Oishi, T. Tetrahedron Lett. 1985, 24, 6461; (b)
Nakata, T.; Nagao, S.; Oishi, T. Tetrahedron Lett. 1985, 26, 6465.
7.52–7.50 (m, 2H), 7.38–7.33 (m, 3H), 5.90–5.79 (m, 1H), 5.49 (s, 1H), 5.09–
4.99 (m, 2H), 4.22 (br d, J = 12.5 Hz, 1H), 4.07 (dd, J = 12.5, 2.0 Hz, 1H), 3.98 (dd,
J = 2.0, 2.0 Hz, 1H), 3.65 (dd, J = 12.0, 3.5 Hz, 1H), 3.63 (br s, 1H), 3.42 (s, 3H),
2.98 (br d, J = 2.0 Hz, 1H), 2.91–2.82 (m, 1H), 2.25–2.19 (m, 1H), 1.33 (s, 3H),
0.96 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 138.1, 136.5, 128.7, 128.0, 126.3,
115.2, 101.5, 84.5, 80.9, 73.1, 70.6, 59.3, 59.1, 35.6, 32.2, 27.8, 22.6; HRMS (FAB)
calcd for C19H27O4 (M+H+) 319.1904, found 319.1907.
7. (a) Willson, T. M.; Kocienski, P.; Faller, A.; Campbell, S. J. Chem. Soc., Chem.
Commun. 1987, 106; (b) Willson, T. M.; Kocienski, P.; Jarowicki, K.; Isaac, K.;
Faller, A.; Campbell, S. F.; Bordner, J. Tetrahedron 1990, 46, 1757; (c) Willson, T.
M.; Kocienski, P.; Jarowicki, K.; Isaac, K.; Hitchcock, P. M.; Faller, A.; Campbell,
S. F. Tetrahedron 1990, 46, 1767; (d) Kocienski, P.; Jarowicki, M.; Marczak, S.
Synthesis 1991, 1191. See also, Ref. 18a,b..
8. Takemura, T.; Nishii, Y.; Takahashi, S.; Kobayashi, J.; Nakata, T. Tetrahedron
2002, 58, 6359.
9. Jewett, J. C.; Rawal, V. H. Angew. Chem., Int. Ed. 2007, 46, 6502.
10. Hong, C. Y.; Kishi, Y. J. Org. Chem. 1990, 55, 4242.
11. (a) Nakata, T.; Matsukura, H.; Jian, D. L.; Nagashima, H. Tetrahedron Lett. 1994,
35, 8229; (b) Nakata, T.; Fukui, H.; Nakagawa, T.; Matsukura, H. Heterocycles
1996, 42, 159; Synthesis of artificial analogues of mycalamide A: (c) Fukui, H.;
Tsuchiya, Y.; Fujita, K.; Nakagawa, T.; Koshino, H.; Nakata, T. Bioorg. Med. Chem.
Lett. 1997, 7, 2081; (d) Takahashi, S.; Okada, A.; Nakata, T. Heterocycles 2004,
27. Data for 13: ½a D23
ꢁ
+59.5 (c 1.03, CHCl3), IR (neat) 3469, 3067, 3031, 2933, 1641,
1497, 1469, 1455, 1389, 1363, 1206, 1173, 1103, 918 cmꢀ1
;
1H NMR (CDCl3,
500 MHz) d 7.36–7.27 (m, 5H), 5.88–5.80 (m, 1H), 5.13–5.08 (m, 2H), 4.69 (d,
J = 11.3 Hz, 1H), 4.58 (d, J = 11.3 Hz, 1H), 4.12 (ddd, J = 9.8, 6.7, 5.2 Hz, 1H), 3.90
(ddd, J = 11.9, 9.8, 2.4 Hz, 1H), 3.79–3.74 (m, 2H), 3.57 (s, 3H), 3.27 (dd, J = 10.4,
2.1 Hz, 1H), 2.96 (d, J = 9.5 Hz, 1H), 2.22–2.18 (m, 1H), 2.13–2.09 (m, 1H), 2.04
(dd, J = 9.2, 2.4 Hz, 1H, OH), 0.97 (s, 3H), 0.89 (s, 3H); 13C NMR (100 MHZ,
CDCl3) d 138.0, 135.9, 129.5, 128.3, 127.7, 127.6, 117.0, 85.5, 77.7, 76.6, 73.2,
69.9, 62.1, 58.5, 41.1, 33.2, 14.3, 14.2; HRMS (FAB) calcd for C19H29O4 (M+H+)
321.2060, found 321.2065.