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Volumn 131, Issue 1, 2009, Pages 78-88

Mechanistic studies on the copper-catalyzed N-arylation of amides

Author keywords

[No Author keywords available]

Indexed keywords

AMIDATE; ARYL HALIDES; ARYL IODIDES; ARYLATION; CATALYTIC REACTIONS; CATALYTIC SPECIES; CHELATING DIAMINES; CONCENTRATION OF; EFFICIENT METHOD; KINETIC STUDY; MECHANISTIC STUDIES; N-ARYLATION;

EID: 62649152953     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0781893     Document Type: Article
Times cited : (297)

References (95)
  • 5
    • 0345329013 scopus 로고    scopus 로고
    • For an older review highlighting the application of the Ullmann/Goldberg reaction in synthesis, see: Lindley, J. Tetrahedron 1984, 40, 1433.
    • For an older review highlighting the application of the Ullmann/Goldberg reaction in synthesis, see: Lindley, J. Tetrahedron 1984, 40, 1433.
  • 6
    • 24144441333 scopus 로고    scopus 로고
    • Palladium-Catalyzed Aromatic Carbon- Nitrogen Bond Formation
    • For reviews on palladium-catalyzed C-N bond formation, see: a, 2nd ed, de Meijere, A, Diederich, F, Eds, Wiley-VCH: Weinheim
    • For reviews on palladium-catalyzed C-N bond formation, see: (a) Jiang, L.; Buchwald, S. L. Palladium-Catalyzed Aromatic Carbon- Nitrogen Bond Formation. In Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; de Meijere, A., Diederich, F., Eds.; Wiley-VCH: Weinheim, 2004; p 699.
    • (2004) Metal-Catalyzed Cross-Coupling Reactions , pp. 699
    • Jiang, L.1    Buchwald, S.L.2
  • 35
    • 9644277114 scopus 로고    scopus 로고
    • For a critical review concerning copper-catalyzed cross coupling reactions, see
    • For a critical review concerning copper-catalyzed cross coupling reactions, see: Beletskaya, I. P.; Cheprakov, A. V. Coord. Chem. Rev. 2004, 248, 2337.
    • (2004) Coord. Chem. Rev , vol.248 , pp. 2337
    • Beletskaya, I.P.1    Cheprakov, A.V.2
  • 48
    • 67849132776 scopus 로고    scopus 로고
    • Ph.D. Thesis, Massachusetts Institute of Technology
    • (b) Strieter, E. R., Ph.D. Thesis, Massachusetts Institute of Technology, 2005.
    • (2005)
    • Strieter, E.R.1
  • 50
    • 84869555771 scopus 로고    scopus 로고
    • This time lapse manifests itself as a plateau in the concentration vs time profiles; thus, in some of the figures, e.g, Figures 4-6, the data at the beginning of the reaction is not shown. Moreover, in some instances, an induction period lasting until approximately 15% conversion is observed. The length of the induction period, i.e, whether it lasts until 5% conversion or until 15% conversion, was not always reproducible. The method in which the inorganic base was dried and stored clearly had an effect on this induction period, and reproducible results for the remainder of the reaction, once the induction period subsided, were only obtained with K3PO4 available from Fluka catalog number 04347, Riedel-de Haën product; free-flowing, fine granules of uniform size, K3PO4 was dried under high vacuum at 150 °C for 3 days and stored in a nitrogen-filled glovebox. Based on these observations, we suspect that the induction period is not m
    • 4 was dried under high vacuum at 150 °C for 3 days and stored in a nitrogen-filled glovebox. Based on these observations, we suspect that the induction period is not mechanistically relevant.
  • 51
    • 67849103161 scopus 로고    scopus 로고
    • Due to the limited solubility of K3PO4 in toluene, it is difficult to estimate the concentrations. Thus, the values for [K 3PO4]0 are reported in millimoles of K 3PO4 used in the reaction
    • 4 used in the reaction.
  • 52
    • 84869579450 scopus 로고    scopus 로고
    • 2 are adjustable parameters.
    • 2 are adjustable parameters.
  • 53
  • 58
    • 67849123748 scopus 로고    scopus 로고
    • Enantiomerically pure (R,R)-3 was used to obtain X-ray quality crystals.
    • Enantiomerically pure (R,R)-3 was used to obtain X-ray quality crystals.
  • 59
    • 84869579448 scopus 로고    scopus 로고
    • total. These results suggest that the dimeric complex is not a kinetically relevant species.
    • total. These results suggest that the dimeric complex is not a kinetically relevant species.
  • 64
    • 4243785018 scopus 로고    scopus 로고
    • Eriksson, H.; Hå&kansson, M. Organometallics 1997, 16, 4243.
    • (e) Eriksson, H.; Hå&kansson, M. Organometallics 1997, 16, 4243.
  • 65
    • 0000510143 scopus 로고    scopus 로고
    • For the synthesis of copper(I)-amides, see: (a) Tsuda, T.; Watanabe, K.; Miyata, K.; Yamamoto, H.; Saegusa, T. Inorg. Chem. 1981, 20, 2728.
    • For the synthesis of copper(I)-amides, see: (a) Tsuda, T.; Watanabe, K.; Miyata, K.; Yamamoto, H.; Saegusa, T. Inorg. Chem. 1981, 20, 2728.
  • 68
    • 67849107861 scopus 로고    scopus 로고
    • A similar procedure was used to characterize Cu(I) alkoxides; see ref 20
    • (32) A similar procedure was used to characterize Cu(I) alkoxides; see ref 20.
  • 74
    • 0002522541 scopus 로고
    • Experimental Organometallic Chemistry: A Practice in Synthesis and Characterization
    • Wayada, A. L, Darensbourg, M. Y, Eds, American Chemical Society, Washington, DC, Chapter 4, pp
    • (b) Burger, B. J.; Bercaw, J. E. In Experimental Organometallic Chemistry: A Practice in Synthesis and Characterization, Wayada, A. L., Darensbourg, M. Y., Eds.; ACS Symposium Series 357: American Chemical Society, Washington, DC, 1987: Chapter 4, pp 94-96.
    • (1987) ACS Symposium Series , vol.357 , pp. 94-96
    • Burger, B.J.1    Bercaw, J.E.2
  • 76
    • 84869555764 scopus 로고    scopus 로고
    • Arylation of Cu(I) amidate in the absence of 3 did not proceed at temperatures between 0 and 90 °C.
    • (36) Arylation of Cu(I) amidate in the absence of 3 did not proceed at temperatures between 0 and 90 °C.
  • 77
    • 84869575784 scopus 로고    scopus 로고
    • 3-ligated Cu(I) amidates also undergo N-arylations; however, these reactions were not kinetically characterized either stoichiometrically or in the context of a catalytic reaction.
    • 3-ligated Cu(I) amidates also undergo N-arylations; however, these reactions were not kinetically characterized either stoichiometrically or in the context of a catalytic reaction.
  • 92
    • 33749129825 scopus 로고    scopus 로고
    • For studies demonstrating the relative affinities of aromatic acids to Cu(I), see: (a) Saphier, M.; Burg, A.; Sheps, S.; Cohen, H.; Meyerstein, D. J. Chem. Soc., Dalton Trans. 1999, 1845.
    • For studies demonstrating the relative affinities of aromatic acids to Cu(I), see: (a) Saphier, M.; Burg, A.; Sheps, S.; Cohen, H.; Meyerstein, D. J. Chem. Soc., Dalton Trans. 1999, 1845.
  • 94
    • 67849132021 scopus 로고    scopus 로고
    • While this manuscript was being prepared, ref 23 was published, which provides experimental evidence that an intermediate such as C in Scheme 4 is unreactive toward aryl iodides and aryl bromides
    • While this manuscript was being prepared, ref 23 was published, which provides experimental evidence that an intermediate such as C in Scheme 4 is unreactive toward aryl iodides and aryl bromides.
  • 95
    • 67849113603 scopus 로고    scopus 로고
    • Nonlinear least-squares fits to eq 9 were obtained by using the Solver function within Microsoft Excel.
    • Nonlinear least-squares fits to eq 9 were obtained by using the Solver function within Microsoft Excel.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.