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Volumn 127, Issue 21, 2005, Pages 7774-7780

One-pot synthesis of metalated pyridines from two acetylenes, a nitrile, and a titanium(II) alkoxide

Author keywords

[No Author keywords available]

Indexed keywords

METALLIZING; NITROGEN COMPOUNDS; TITANIUM COMPOUNDS;

EID: 19744363604     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja050261e     Document Type: Article
Times cited : (118)

References (76)
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    • Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford
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    • (f) Schore, N. E. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, pp 1129-1162.
    • (1991) Comprehensive Organic Synthesis , vol.5 , pp. 1129-1162
    • Schore, N.E.1
  • 15
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    • Wakatsuki, Y.; Yamazaki, H. J. Chem. Soc., Dalton Trans. 1978, 1278-1282. There had been no reports on the selective cyclotrimerization of two different, unsymmetrical acetylenes and a nitrile before we and others reported such examples (see refs 4 and 5).
    • (1978) J. Chem. Soc., Dalton Trans. , pp. 1278-1282
    • Wakatsuki, Y.1    Yamazaki, H.2
  • 16
    • 0000985185 scopus 로고
    • For recent reports, which deal with cyclotrimerization of the same (ref 3a-h), symmetrical (ref 3i), or tethered (ref 3j-p) substrates, see: (a) Bianchini, C; Meli, A.; Peruzzini, M.; Vacca, A.; Vizza, F. Organometallics 1991, 10, 645-651.
    • (1991) Organometallics , vol.10 , pp. 645-651
    • Bianchini, C.1    Meli, A.2    Peruzzini, M.3    Vacca, A.4    Vizza, F.5
  • 32
    • 0037051610 scopus 로고    scopus 로고
    • Suzuki, D.; Tanaka, R.; Urabe, H.: Sato, F. J. Am. Chem. Soc. 2002, 124, 3518-3519. Portions of type-A and type-D reactions in Scheme I have been reported in this communication.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 3518-3519
    • Suzuki, D.1    Tanaka, R.2    Urabe, H.3    Sato, F.4
  • 43
    • 19744366174 scopus 로고    scopus 로고
    • note
    • p-Toluenesulfonylnitrile is commercially available.
  • 45
  • 46
    • 0002206611 scopus 로고
    • Schlosser, M., Ed.: Wiley: Chichester
    • Reetz, M. T. In Organometallics in Synthesis; Schlosser, M., Ed.: Wiley: Chichester, 1994: pp 195-282.
    • (1994) Organometallics in Synthesis , pp. 195-282
    • Reetz, M.T.1
  • 48
    • 19744361925 scopus 로고    scopus 로고
    • note
    • However, the intermediates in this scheme so far remain unidentified.
  • 49
    • 19744373017 scopus 로고    scopus 로고
    • note
    • When the reaction was quenched at a lower temperature (-50 °C), sulfonylpyridine 24b became a major constituent (24b and 24a in 37 and 28% yields, respectively).
  • 50
    • 19744365869 scopus 로고    scopus 로고
    • note
    • For additional control experiments and discussion, see the Experimental Section.
  • 57
    • 0034802561 scopus 로고    scopus 로고
    • Sulfonylacetylene and haloacetylene undergo the double addition to titanacyclopropene and the elimination of halide. respectively. See: Suzuki, D.: Urabe, H.; Sato. F. J. Am. Chem. Soc. 2001, 123, 7925-7926.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 7925-7926
    • Suzuki, D.1    Urabe, H.2    Sato, F.3
  • 61
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    • This suggests the importance of the presence of a coordinating moiety in the nitrile. See: ref 4 and the following. Bertus, P.; Szymoniak, J. J. Org. Chem. 2002, 67, 3965-3968.
    • (2002) J. Org. Chem. , vol.67 , pp. 3965-3968
    • Bertus, P.1    Szymoniak, J.2
  • 62
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    • Nonetheless, as α-oxynitriles and their derivatives are readily obtained by the cyanohydrin synthesis and its modifications, this reaction will find reasonable application. See: North, N., Ed. Tetrahedron (Symposium-in-Print) 2004, 60, 10385-10568.
    • (2004) Tetrahedron (Symposium-in-Print) , vol.60 , pp. 10385-10568
    • North, N.1
  • 63
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    • For examples of elimination of a leaving group on nitrogen by a neighboring carbanionic site, see: Schönberg, A.; Moubacher, R. Chem. Rev. 1952, 50, 261-277.
    • (1952) Chem. Rev. , vol.50 , pp. 261-277
    • Schönberg, A.1    Moubacher, R.2
  • 71
    • 0002679715 scopus 로고
    • For the generation of carbonyl group-group 4 metal complexes and their synthetic application, see: Erker, G.; Rosenfeldt, F. J. Organomet. Chem. 1982, 224, 29-42.
    • (1982) J. Organomet. Chem. , vol.224 , pp. 29-42
    • Erker, G.1    Rosenfeldt, F.2
  • 76
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    • note
    • This may come from lower α acidity of 90 as compared to that of 44 or 84. Moreover, the irreversible elimination of the most reactive bromo group (among 90, 44, and 84) from titanated 90 should force the titanium transfer reaction from 91 to 90.


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