Pd(II)-catalyzed cyclization to ether and its application to the synthesis of the trans-fused polyether core

Heterocycles

Volumn 77, Issue 1, 2009, Pages 211-215

  Yokoyama, Hajime ^a   Nakayama, Satoshi ^a   Murase, Masayuki ^a   Miyazawa, Masahiro ^a   Yamaguchi, Seiji ^a   Hirai, Yoshiro ^a  

^a UNIVERSITY OF TOYAMA   (Japan)

Author keywords

Cyclization; Palladium Catalyst; Polyether; Synthesis

Indexed keywords

EID: 65549141523     PISSN: 03855414     EISSN: None     Source Type: Journal    
DOI: 10.3987/COM-08-S(F)36     Document Type: Article

References (26)

1. Blunt J.W., Copp B.R., Murro M.H.G., Northcote P.T., and Prinsep M.R. Nat. Prod. Rep. 21 (2004) 1-49
2. Faulkner D.J. Nat. Prod. Rep. 19 (2002) 1-48
3. Yasumoto T. Chem. Rec. 1 (2001) 228
4. Scheuer P.J. Tetrahedron 50 (1994) 3
5. Kadota I., and Yamamoto Y. Acc. Chem. Res. 38 (2005) 423
6. Nakata T. Chem. Rev. 105 (2005) 4314
7. Inoue M. Chem. Rev. 105 (2005) 4379
8. Selected iterative synthesis. Trost B.M., and Rhee Y.H. Org. Lett. 6 (2004) 4311
9. Mori Y., Yaegashi K., and Furukawa H. J. Am. Chem. Soc. 118 (1996) 8158
10. Hori N., Matsukura H., Matsuo G., and Nakata T. Tetrahedron Lett. 40 (1999) 2811
11. Harirington P.J., Hegedus L.S., and McDaniel K.F. J. Am. Chem. Soc. 109 (1987) 4335
12. Saito S., Hara T., Takahashi N., Hirai M., and Moriwake T. Synlett (1992) 237
13. Makabe H., Kong L.K., and Hirota M. Org. Lett. 5 (2003) 27
14. Uenishi J., Ohmi M., and Ueda A. Tetrahedron: Asymmetry 16 (2005) 1299
15. Hirai Y., Terada T., Amemiya Y., and Momose T. Tetrahedron Lett 33 (1992) 7893
16. Hirai Y., and Nagatsu M. Chem. Lett. (1994) 21
17. Hirai Y., Shibuya K., Fukuda Y., Yokoyama H., and Yamaguchi S. Chem. Lett (1997) 22
18. Hirai Y., Watanabe J., Nozaki T., Yokoyama H., and Yamaguchi S. J. Org. Chem. 62 (1997) 776
19. Yokoyama H., Otaya K., Yamaguchi S., and Hirai Y. Tetrahedron Lett. 39 (1998) 5971
20. Yokoyama H., Otaya K., Kobayashi H., Miyazawa M., Yamaguchi S., and Hirai Y. Org. Lett. 2 (2000) 2427
21. Miyazawa M., Hirose Y., Narantsetseg M., Yokoyama H., Yamaguchi S., and Hirai Y. Tetrahedron Lett. 45 (2004) 2883
22. Miyazawa M., Narantsetseg M., Yokoyama H., Yamaguchi S., and Hirai Y. Heterocycles 63 (2004) 1017
23. Nicolaou K.C., Hwang C.-K., Marron B.E., Defrees S.A., Couladouros E.A., Abe Y., Carroll P.J., and Snyder J.P. J. Am. Chem. Soc 112 (1990) 3040
24. We concluded the Pd(II)-catalyzed cyclization proceeded with high stereoselectivity because the alcohol (5) was oxidized by IBX to give the ketones as a >82 : 18 ratio(by NMR analysis). These good stereoselectivities can be explained by cyclic transition model as shown below (Figure 2). It is likely that two chair-form transition states are involved. The transition state A, leading to the major product, would be more stable than the transition state B, which is subject to steric repulsion between the π-allyloxy palladium complex and the axial proton on another ring. {A figure is presented}
25. 3) δ 5.84 (ddd, J=17.2, 10.6, 7.3 Hz, 1H), 5.43 (dt, J=17.2, 0.7Hz, 1H), 5.36 (dt, J= 10.6, 0.7 Hz, 1H), 3.93-3.91 (m, 1H), 3.59-3.56 (m, 1H), 3.45 (ddd, J=l 1.4, 9.2, 4.4Hz, 1H), 3.39 (dt, J=1 1.4, 3.7Hz, 1H), 3.09-3.02 (m, 2H), 2.41 (ddd, J= 11.4, 4.4, 4.4Hz, 1H), 2.11-2.07 (m, 1H), 1.74-1.71 (m, 2H), 1.58 (brs, 1H), 1.55-1.50 (m, 1H), 1.43 (ddd, J=23.1, 11.7, 5.5Hz, 1H).
26. 3) δ 5.84 (ddd, J=17.6, 10.6, 7.3 Hz, 1H), 5.44 (dt, J=17.6, 1.5 Hz, 1H), 5.37 (dt, J=10.6, 1.5 Hz, 1H), 3.92 (ddt, J=11.4, 4.0, 1.8 Hz, 1H), 3.57 (dd, J=7.3Hz, 1H), 3.45 (ddd, J=l 1.0, 9.2, 4.8 Hz, 1H), 3.39 (dt, J=11.4,4.0Hz, 1H), 3.17-3.11 (m,2H), 3.09-3.03 (m, 2H), 2.45 (ddd, J=l 1.4, 4.0, 4.0 Hz, 1H), 2.34 (ddd, J=l 1.4, 4.0, 4.0 Hz, 1H), 2.10-2.06 (m, 2H), 1.75-1.72 (m, 3H), 1.55-1.51 (m, 2H).