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Volumn 130, Issue 6, 2008, Pages 1820-1821

Copper-catalyzed 1,2-double amination of 1-halo-1-alkynes. Concise synthesis of protected tetrahydropyrazines and related heterocyclic compounds

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE; HALIDE; HETEROCYCLIC COMPOUND; PYRAZINE DERIVATIVE; TETRAHYDROPYRAZINE DERIVATIVE; UNCLASSIFIED DRUG;

EID: 39049136011     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja078163b     Document Type: Article
Times cited : (126)

References (29)
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  • 2
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    • Katritzky, A. R, Rees, C. W, Eds, Pergamon Press: Oxford
    • (b) Sainsburg, M. Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Eds.; Pergamon Press: Oxford, 1984; Vol 3, pp 995-1038.
    • (1984) Comprehensive Heterocyclic Chemistry , vol.3 , pp. 995-1038
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    • Katritzky, A. R, Rees, C. W, Eds, Pergamon Press: Oxford
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    • (d) Katritzky, A. R., Ed. Chem. Rev. 2004, 104, 2125-2812.
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    • Double amination of olefins leading to the direct formation of diazacycies has been recently reported: (a) Hamaguchi, H, Kosaka, S, Ohno, H, Tanaka, T. Angew. Chem, Int. Ed. 2005, 44, 1513-1517
    • Double amination of olefins leading to the direct formation of diazacycies has been recently reported: (a) Hamaguchi, H.; Kosaka, S.; Ohno, H.; Tanaka, T. Angew. Chem., Int. Ed. 2005, 44, 1513-1517.
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    • However, the same type of reaction across an acetylenic bond is rare. For example, see: e
    • However, the same type of reaction across an acetylenic bond is rare. For example, see: (e) Lipshutz, B. H.; Taft, B. R. Angew. Chem., Int. Ed. 2006, 45, 8235-8238.
    • (2006) Angew. Chem., Int. Ed , vol.45 , pp. 8235-8238
    • Lipshutz, B.H.1    Taft, B.R.2
  • 10
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    • For a recent preparation of similar heterocycles starting with terminal acetylenes via olefin isomerization, see: Zulys, A, Dochnahl, M, Hollmann, D, Löhnwitz, K, Herrmann, J.-S, Roesky, P. W, Blechert, S. Angew. Chem, Int. Ed. 2005, 44, 7794-7798
    • For a recent preparation of similar heterocycles starting with terminal acetylenes via olefin isomerization, see: Zulys, A.; Dochnahl, M.; Hollmann, D.; Löhnwitz, K.; Herrmann, J.-S.; Roesky, P. W.; Blechert, S. Angew. Chem., Int. Ed. 2005, 44, 7794-7798.
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    • For details, see the Supporting Information
    • For details, see the Supporting Information.
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    • 2 (R = Ac or Boc) did not give such products. For deprotection of sulfonamides, see: Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991; pp 379-385.
    • 2 (R = Ac or Boc) did not give such products. For deprotection of sulfonamides, see: Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991; pp 379-385.
  • 17
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    • The direction of this ring closure (paths a or b) is hardly predictable a priori based on the available data such as those in refs 8 and 9.
    • The direction of this ring closure (paths a or b) is hardly predictable a priori based on the available data such as those in refs 8 and 9.
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    • Both 6-endo-dig and 5-exo-dig are favorable modes for ring closure. For Baldwin's rule, see: (a) Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734-736.
    • Both 6-endo-dig and 5-exo-dig are favorable modes for ring closure. For Baldwin's rule, see: (a) Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734-736.
  • 19
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    • For 5-exo-dig cyclization with a nitrogen nucleophile, see: (b) Schomaker, J. M.; Geiser, A. R.; Huang, R.; Borhan, B. J. Am. Chem. Soc. 2007, 129, 3794-3795.
    • For 5-exo-dig cyclization with a nitrogen nucleophile, see: (b) Schomaker, J. M.; Geiser, A. R.; Huang, R.; Borhan, B. J. Am. Chem. Soc. 2007, 129, 3794-3795.
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    • For 6-endo-dig cyclization, see: (c) Yanada, R.; Obika, S.; Kono, H.; Takemoto, Y. Angew. Chem., Int. Ed. 2006, 45, 3822-3825.
    • For 6-endo-dig cyclization, see: (c) Yanada, R.; Obika, S.; Kono, H.; Takemoto, Y. Angew. Chem., Int. Ed. 2006, 45, 3822-3825.
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    • A nucleophile could be introduced to either 1- or 2-position of 1-(sulfonylamino)-1-alkynes depending upon the kind of reactions. For a reaction at the 1-position, see: (a) Zhang, Y.; Hsung, R. P.; Zhang, X.; Huang, J.; Slafer, B. W.; Davis, A. Org. Lett. 2005, 7, 1047-1050.
    • A nucleophile could be introduced to either 1- or 2-position of 1-(sulfonylamino)-1-alkynes depending upon the kind of reactions. For a reaction at the 1-position, see: (a) Zhang, Y.; Hsung, R. P.; Zhang, X.; Huang, J.; Slafer, B. W.; Davis, A. Org. Lett. 2005, 7, 1047-1050.
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    • For reviews on the chemistry of (1-alkynyl)amine derivatives, see: c
    • For reviews on the chemistry of (1-alkynyl)amine derivatives, see: (c) Katritzky, A. R.; Jiang, R.; Singh, S. K. Heterocycles 2004, 63, 1455-1475.
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    • (e) Hsung, R. P., Ed. Tetrahedron 2006, 62, 3783-3938.
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    • This outcome is consistent with that of the closely related cyclization of ref 8b. For reviews on hydroamination of alkynes, see: (a) Alonso, F, Beletskaya, I. P, Yus, M. Chem. Rev. 2004, 104, 3079-3159
    • This outcome is consistent with that of the closely related cyclization of ref 8b. For reviews on hydroamination of alkynes, see: (a) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079-3159.
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    • A normal double coupling of 1,1-dibromoolefin with a diamine derivative was also reported: Yuen, J.; Fang, Y.-Q.; Lautens, M. Org. Lett. 2006, 8, 653-656. The different substrate structures and reaction media may account for the change in the type of products.
    • A normal double coupling of 1,1-dibromoolefin with a diamine derivative was also reported: Yuen, J.; Fang, Y.-Q.; Lautens, M. Org. Lett. 2006, 8, 653-656. The different substrate structures and reaction media may account for the change in the type of products.


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