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Volumn 130, Issue 46, 2008, Pages 15304-15310

1,3-Dipolar cycloaddition of organic azides to alkynes by a dicopper-substituted silicotungstate

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE; AROMATIC HYDROCARBONS; COPPER; CYCLOADDITION; HYDROCARBONS; ORGANIC POLYMERS; SODIUM; SUGAR (SUCROSE);

EID: 56449130666     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja806249n     Document Type: Article
Times cited : (158)

References (53)
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    • (2000) J. Med. Chem , vol.43 , pp. 953-970
    • Genin, M.J.1
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    • 5c
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    • (c) Hill, C. L. Chem. Rev. 1998, 98, 1-390.
    • (1998) Chem. Rev , vol.98 , pp. 1-390
    • Hill, C.L.1
  • 33
    • 56449123352 scopus 로고    scopus 로고
    • The reaction rate for the [(SIMes)CuBr]-catalyzed cycloaddition of 1a to 2a in DMSO showed a first-order dependence on the concentration of [(SIMes)CuBr] (6.5-50.4 mM, see Supporting Information). In the case of [(SIMes)CuBr], the cycloaddition of internal alkynes efficiently proceeded. On the other hand, no cycloaddition of internal alkynes proceeded in the presence of the precatalyst I. The discrepancy suggests that the [(SIMes)CuBr]-catalyzed cyclization likely proceeds in a different way in comparison with the I-mediated cycloaddition.
    • The reaction rate for the [(SIMes)CuBr]-catalyzed cycloaddition of 1a to 2a in DMSO showed a first-order dependence on the concentration of [(SIMes)CuBr] (6.5-50.4 mM, see Supporting Information). In the case of [(SIMes)CuBr], the cycloaddition of internal alkynes efficiently proceeded. On the other hand, no cycloaddition of internal alkynes proceeded in the presence of the precatalyst I. The discrepancy suggests that the [(SIMes)CuBr]-catalyzed cyclization likely proceeds in a different way in comparison with the I-mediated cycloaddition.
  • 47
    • 56449115700 scopus 로고    scopus 로고
    • After the reaction was completed, the precipitate was recovered by addition of an excess amount of toluene (precipitation method) to the reaction solution. The copper content in the filtrate was less than 1% of that in fresh I, indicating that the copper species hardly leaches into the reaction solution. The elemental analysis and 1H NMR spectrum of the recovered precipitate showed that the recovered I consists of one molecule of dicopper-substituted silicotungstate and two molecules of 3a. The UV-vis spectrum of the recovered I agreed well with that of the sum of fresh I and 3a, suggesting that the γ-Keggin structure of the recovered I is retained after the cycloaddition. No absorption bands at 700 nm due to the d-d transition of the copper(II) species was observed in the UV-vis spectrum of the recovered I, suggesting the presence of the reduced copper(I) species in the recovered I
    • 1H NMR spectrum of the recovered precipitate showed that the recovered I consists of one molecule of dicopper-substituted silicotungstate and two molecules of 3a. The UV-vis spectrum of the recovered I agreed well with that of the sum of fresh I and 3a, suggesting that the γ-Keggin structure of the recovered I is retained after the cycloaddition. No absorption bands at 700 nm due to the d-d transition of the copper(II) species was observed in the UV-vis spectrum of the recovered I, suggesting the presence of the reduced copper(I) species in the recovered I.
  • 49
    • 0004055425 scopus 로고
    • 3rd ed, Perrin, D. D, Armarego, W. L. F, Eds, Pergamon Press: Oxford, U.K
    • Purification of Laboratory Chemicals, 3rd ed.; Perrin, D. D., Armarego, W. L. F., Eds.; Pergamon Press: Oxford, U.K., 1988.
    • (1988) Purification of Laboratory Chemicals
  • 53
    • 56449113482 scopus 로고    scopus 로고
    • Frisch, M. J. et al. Gaussian 03, revision D.02; Gaussian, Inc.: Wallingford, CT, 2004.
    • Frisch, M. J. et al. Gaussian 03, revision D.02; Gaussian, Inc.: Wallingford, CT, 2004.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.