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Volumn 127, Issue 17, 2005, Pages 6284-6289

A highly enantio- and diastereoselective catalytic intramolecular Stetter reaction

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; MOLECULES; SUBSTITUTION REACTIONS;

EID: 18244367138     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0425132     Document Type: Article
Times cited : (250)

References (74)
  • 12
    • 0001070365 scopus 로고
    • Paquette, L. A., Ed.; Wiley: New York
    • (a) Stetter, H.; Kuhlmann, H. In Organic Reactions; Paquette, L. A., Ed.; Wiley: New York, 1991; Vol. 40, pp 407-496.
    • (1991) Organic Reactions , vol.40 , pp. 407-496
    • Stetter, H.1    Kuhlmann, H.2
  • 20
    • 0000679263 scopus 로고    scopus 로고
    • Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, Chapter 31.1
    • (a) Tomioka, K.; Nagaoka, Y. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 3, Chapter 31.1.
    • (1999) Comprehensive Asymmetric Catalysis , vol.3
    • Tomioka, K.1    Nagaoka, Y.2
  • 21
    • 0000957502 scopus 로고    scopus 로고
    • Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, Chapter 31.2
    • (b) Yamaguchi, M. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 3, Chapter 31.2.
    • (1999) Comprehensive Asymmetric Catalysis , vol.3
    • Yamaguchi, M.1
  • 22
    • 0034612973 scopus 로고    scopus 로고
    • and references therein
    • (c) Sibi, M. P.; Manyem, S. Tetrahedron 2000, 56, 8033-8061 and references therein.
    • (2000) Tetrahedron , vol.56 , pp. 8033-8061
    • Sibi, M.P.1    Manyem, S.2
  • 39
    • 0033828529 scopus 로고    scopus 로고
    • For selective examples of conjugate addition/tandem reactions of chiral nucleophiles, see: (a) Hanessian, S.; Gomtsyan, A.; Malek, N. J. Org. Chem. 2000, 65, 5623-5631.
    • (2000) J. Org. Chem. , vol.65 , pp. 5623-5631
    • Hanessian, S.1    Gomtsyan, A.2    Malek, N.3
  • 41
    • 0035955146 scopus 로고    scopus 로고
    • For example of tandem radical reactions, see: Sibi, M. P.; Chen, J. J. Am. Chem. Soc. 2001, 123, 9472-9473.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 9472-9473
    • Sibi, M.P.1    Chen, J.2
  • 42
    • 0033599528 scopus 로고    scopus 로고
    • For examples of concerted conjugate addition to Michael acceptors, see: (a) Niu, D.; Zhao, K. J. Am. Chem. Soc. 1999, 121, 2456-2459.
    • (1999) J. Am. Chem. Soc. , vol.121 , pp. 2456-2459
    • Niu, D.1    Zhao, K.2
  • 58
    • 15844390521 scopus 로고
    • For related examples that study the approach of electrophiles on carbon-carbon double bond adjacent to a stereogenic center, see: (b) Paddon-Row, M. N.; Rondan, N. G.; Houk, K. N. J. Am. Chem. Soc. 1982, 104, 7162-7166.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 7162-7166
    • Paddon-Row, M.N.1    Rondan, N.G.2    Houk, K.N.3
  • 62
    • 3142640259 scopus 로고
    • For the mechanism of the thiamine-catalyzed benzoin condensation reaction, see: (a) Breslow, R. J. Am. Chem. Soc. 1958, 80, 3719-3726.
    • (1958) J. Am. Chem. Soc. , vol.80 , pp. 3719-3726
    • Breslow, R.1
  • 65
    • 18244402611 scopus 로고
    • Mechanism of the cyanide-catalyzed reaction, see: (d) Lapworth, A. J. Am. Chem. Soc. 1903, 83, 995.
    • (1903) J. Am. Chem. Soc. , vol.83 , pp. 995
    • Lapworth, A.1
  • 67
    • 18244392652 scopus 로고    scopus 로고
    • note
    • See Experimental Section for generation of the free carbene.
  • 68
    • 18244376570 scopus 로고    scopus 로고
    • note
    • We have shown that varying the electronic nature of the catalyst can have an affect on reactivity and selectivity; see ref 4c.
  • 69
    • 18244389184 scopus 로고    scopus 로고
    • note
    • The exact mode of the epimerization is still under investigation.
  • 70
    • 18244394777 scopus 로고    scopus 로고
    • note
    • See Supporting Information for crystal structure data.
  • 71
    • 18244383012 scopus 로고    scopus 로고
    • note
    • For examples of the reverse Cope elimination mechanism of hydroxylamine additions, see ref 11.
  • 72
    • 18244382767 scopus 로고    scopus 로고
    • note
    • Further support for the intramolecular proton-transfer event was gained by conducting the reactions at various concentrations. Lowering the reaction concentration from 0.3 to 0.02 M increased the diastereoselectivity from 10:1 to 30:1. The reactions were monitored by GC analysis over the course of 24 h and the diastereoselectivity remained constant for each reaction, suggesting that a bimolecular event leads to a slight degradation of selectivity. However, it cannot be ruled out that higher concentration leads to a greater amount of epimerization.
  • 73
    • 18244407498 scopus 로고    scopus 로고
    • note
    • As mentioned above, it is also possible that the α-hydroxy-α- azolium anion adds to the Michael acceptor in concerted fashion, analogous to the reverse Cope elimination mechanism seen with hydroxylamine additions.
  • 74
    • 18244393142 scopus 로고    scopus 로고
    • note
    • 4 salt, which was prepared according to general procedure, through a Gelman 0.45 μm filter.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.