Efficient pinacol rearrangement mediated by trimethyl orthoformate

Tetrahedron Letters

Volumn 38, Issue 48, 1997, Pages 8315-8318

  Kita, Yasuyuki ^a   Yoshida, Yutaka ^a   Mihara, Sachiko ^a   Fang, Dai Fei ^a   Higuchi, Kazuhiro ^a   Furukawa, Akihiro ^a   Fujioka, Hiromichi ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; PINACOL DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; REACTION ANALYSIS; STRUCTURE ACTIVITY RELATION; STRUCTURE ANALYSIS;

EID: 0030695202     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10210-6     Document Type: Article

References (17)

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2. Robertson, G. M."Comprehensive Organic Synthesis"; Trost, B. M.; Fleming, I., Ed., Pergamon Press, Oxford, 1991, Vol. 3, p. 563.
3. Chiara, J. L.; Cabri, W.; Hanessian, S. Tetrahedron Lett. 1991, 32, 1125; Uenishi, J.; Masuda, S.; Wakabayashi, S. Tetrahedron Lett. 1991, 32, 5097; Hamann, B.; Namy, J. L.; Kagan, H. B. Tetrahedron 1996, 52, 14225; Nomura, R.; Matsuno, T.; Endo, T. J. Am. Chem. Soc. 1996, 118, 11666.
4. Chiara, J. L.; Cabri, W.; Hanessian, S. Tetrahedron Lett. 1991, 32, 1125; Uenishi, J.; Masuda, S.; Wakabayashi, S. Tetrahedron Lett. 1991, 32, 5097; Hamann, B.; Namy, J. L.; Kagan, H. B. Tetrahedron 1996, 52, 14225; Nomura, R.; Matsuno, T.; Endo, T. J. Am. Chem. Soc. 1996, 118, 11666.
5. Chiara, J. L.; Cabri, W.; Hanessian, S. Tetrahedron Lett. 1991, 32, 1125; Uenishi, J.; Masuda, S.; Wakabayashi, S. Tetrahedron Lett. 1991, 32, 5097; Hamann, B.; Namy, J. L.; Kagan, H. B. Tetrahedron 1996, 52, 14225; Nomura, R.; Matsuno, T.; Endo, T. J. Am. Chem. Soc. 1996, 118, 11666.
6. Chiara, J. L.; Cabri, W.; Hanessian, S. Tetrahedron Lett. 1991, 32, 1125; Uenishi, J.; Masuda, S.; Wakabayashi, S. Tetrahedron Lett. 1991, 32, 5097; Hamann, B.; Namy, J. L.; Kagan, H. B. Tetrahedron 1996, 52, 14225; Nomura, R.; Matsuno, T.; Endo, T. J. Am. Chem. Soc. 1996, 118, 11666.
7. Haines, A. H."Comprehensive Organic Synthesis", Trost, B. M.; Fleming, I., Ed., Pergamon Press, Oxford, 1991, Vol. 7, p. 437.
8. Harada, T.; Mukaiyama, T. Chem. Lett. 1992, 81.
9. Sands, R. D. J. Org. Chem. 1994, 59, 468.
10. Fujioka, H.; Kitagaki, S.; Imai, R.; Kondo, M.; Okamoto, S.; Yoshida, Y.; Akai, S.; Kita, Y. Tetrahedron Lett. 1995, 36, 3219; Kita, Y.; Kiatagaki, S.; Yoshida, Y.; Mihara, S.; Fang, D. -F.; Fujioka, H. ibid. 1997, 38, 1061.
11. Fujioka, H.; Kitagaki, S.; Imai, R.; Kondo, M.; Okamoto, S.; Yoshida, Y.; Akai, S.; Kita, Y. Tetrahedron Lett. 1995, 36, 3219; Kita, Y.; Kiatagaki, S.; Yoshida, Y.; Mihara, S.; Fang, D. -F.; Fujioka, H. ibid. 1997, 38, 1061.
12. For remarkable effect of acyloxy group on the stability of cationic intermediate, see ref. 7.
13. For the effect of an ortho ester towards the reactions which proceed under dehydrative conditions, see: Fujioka, H.; Kitagawa, H.; Kondo, M.; Matsunaga, N.; Kitagaki, S.; Kita, Y. Heterocycles 1993, 35, 665; Fujioka, H.; Kitagawa, H.; Kondo, M.; Kita, Y. ibid. 1994, 37, 743.
14. For the effect of an ortho ester towards the reactions which proceed under dehydrative conditions, see: Fujioka, H.; Kitagawa, H.; Kondo, M.; Matsunaga, N.; Kitagaki, S.; Kita, Y. Heterocycles 1993, 35, 665; Fujioka, H.; Kitagawa, H.; Kondo, M.; Kita, Y. ibid. 1994, 37, 743.
15. 4, and concentrated. The crude product was purified by column chromatography on silica gel (hexane/ethyl acetate) to give the pure product.
16. Ortho ester A can be easily detected on TLC.
17. Although the formation of another cationic intermediate C might take place, C is disadvantageous for the rearrangement reaction and orthoester A is reproduced with coexistent MeOH, then rearrangement would proceed via B. equation presented [ see: Oikawa, M.; Wada, A.; Okazaki, F.; Kusumoto, S. J. Org. Chem. 1996, 61, 4469.]