Stereoselectivity in 1,3-Dipolar Cycloaddition Reactions of 2-Benzopyrylium-4-olate with Acrylic Acid Derivatives Catalyzed by Rare Earth Metal Triflates

Kei Inoue; Hiroyuki Suga; Shuichi Inoue; Hiroki Sato; Akikazu Kakehi

doi:10.1055/s-2003-40190

SPECIALTOPIC

Stereoselectivity in 1,3-Dipolar Cycloaddition Reactions of 2-Benzopyrylium-4-olate with Acrylic Acid Derivatives Catalyzed by Rare Earth Metal Triflates

Kei Inoue, Hiroyuki Suga*, Shuichi Inoue, Hiroki Sato, Akikazu Kakehi
Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano 380-8553, Japan
e-Mail: sugahio@gipwc.shinshu-u.ac.jp;

Abstract

All articles of this category

Abstract

The addition of Yb(OTf)₃ or Lu(OTf)₃ was found to be quite effective in obtaining exo-selectivity (up to 87:13) in the reaction of 2-benzopyrylium-4-olate, which was generated by the Rh₂(OAc)₄-catalyzed decomposition of o-methoxycarbonyl-α-diazoacetophenone, with 3-acryloyl-2-oxazolizinone. The stereoselectivity of the rare earth metal triflate-catalyzed reaction was strongly influenced by the ionic radius of the rare earth metal element, a larger or smaller ionic radius than that of Lu³⁺ resulted in decreased exo-selectivity.

Key words

1,3-dipolar cycloaddition - carbonyl ylide - rare earth metal triflate - stereoselectivity

Full Text

References

For recent reviews see:

1a In Comprehensive Organic Synthesis Trost BM. Pergamon Press; New York: 1991.

1b Kagan HB. Riant O. Chem. Rev. 1992, 92: 1007

1c In Comprehensive Asymmetric Catalysts Jacobsen EN. Pfaltz A. Yamamoto H. Springer; New York: 1999. and references therein

For reviews see:

2a Kanemasa S. In Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products Padwa A. Pearson WH. John Wiley & Sons; Hoboken: 2003. Chap. 11. p.755

2b Gothelf KV. Jørgensen KA. In Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products Padwa A. Pearson WH. John Wiley & Sons; Hoboken: 2003. Chap. 12. p.817

2c Gothelf KV. Jørgensen KA. Chem. Rev. 1998, 98: 863

For reviews see:

3a MacMills MC. Wright D. In Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles, and Natural Products Padwa A. Pearson WH. John Wiley & Sons; Hoboken: 2003. Chap. 4. p.253

3b Padwa A. Weingarten MD. Chem. Rev. 1996, 96: 223

3c Padwa A. Hornbuckle SF. Chem. Rev. 1991, 91: 263

4a Suga H. Ishida H. Ibata T. Tetrahedron Lett. 1998, 39: 3165

4b Suga H. Kakehi A. Ito S. Inoue K. Ishida H. Ibata T. Bull. Chem. Soc. Jpn. 2001, 74: 1115

4c Suga H. Kakehi A. Ito S. Inoue K. Ishida H. Ibata T. Org. Lett. 2000, 2: 3145

4d Suga H. Inoue K. Inoue S. Kakehi A. J. Am. Chem. Soc. 2002, 124: 14836

5a Ueda K. Ibata T. Takebayashi M. Bull. Chem. Soc. Jpn. 1972, 45: 2779

5b Ibata T. Chem. Lett. 1976, 233

5c Hamaguchi M. Ibata T. Tetrahedron Lett. 1974, 4475

5d Ibata T. Motoyama T. Hamaguchi M. Bull. Chem. Soc. Jpn. 1976, 49: 2298

5e Ibata T. Jitsuhiro K. Bull. Chem. Soc. Jpn. 1979, 52: 3582

5f Ibata T. Jitsuhiro K. Tsubokura Y. Bull. Chem. Soc. Jpn. 1981, 54: 240

5g Tamura H. Ibata T. Ogawa K. Bull. Chem. Soc. Jpn. 1984, 57: 926

5h Ibata T. Toyoda J. Bull. Chem. Soc. Jpn. 1985, 58: 1787

5i Ibata T. Toyoda J. Sawada M. Tanaka T. J. Chem. Soc., Chem. Commun. 1986, 1266

6 Kashima C. Harada H. Kita I. Fukuchi I. Hosomi A. Synthesis 1994, 61

7 Evans DA. Miller SJ. Lectka T. von Matt P. J. Am. Chem. Soc. 1999, 121: 7559

8a (S,S)-Pybox-i-Pr: Totleben MJ. Prasad JS. Simpson JH. Chan SH. Vanyo DJ. Kuehner DE. Deshpande R. Kodersha GA. J. Org. Chem. 2001, 66: 1057

8b See also: Desimoni G. Faita G. Filippone S. Mella M. Zampori MG. Zema M. Tetrahedron 2001, 57: 10203

8c (S,S)-Pybox-Ph: Davies IW. Gerena L. Lu N. Larsen RD. Reider PJ. J. Org. Chem. 1996, 61: 9629

8d (S,S)-Pybox-TBSm: Iwasa S. Nakamura H. Nishiyama H. Heterocycles 2000, 52: 939

9 Shannon RD. Acta Crystallogr., Sect. A 1976, 32: 751