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Volumn 26, Issue 1, 2007, Pages 65-74

Precatalysts involved in copper-catalyzed arylations of nucleophiles

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; CATALYSTS; CHELATION; DIMERS; ELECTROCHEMISTRY; ORGANOMETALLICS; OXIDATION; X RAY CRYSTALLOGRAPHY;

EID: 33846201643     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om060706n     Document Type: Article
Times cited : (85)

References (54)
  • 8
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    • For patents, see: (a) Taillefer, M.; Cristau, H.-J.; Cellier, P. P.; Spindler, J.-F. FR 0116547, 2001.
    • For patents, see: (a) Taillefer, M.; Cristau, H.-J.; Cellier, P. P.; Spindler, J.-F. FR 0116547, 2001.
  • 9
    • 33846209283 scopus 로고    scopus 로고
    • Taillefer, M.; Cristau, H.-J.; Cellier, P. P.; Spindler, J.-F. FR 2833947, 2003; Chem. Abstr. 2003, 139, 69290.
    • (b) Taillefer, M.; Cristau, H.-J.; Cellier, P. P.; Spindler, J.-F. FR 2833947, 2003; Chem. Abstr. 2003, 139, 69290.
  • 11
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    • Taillefer, M.; Cristau, H.-J.; Cellier, P. P.; Spindler, J.-F. FR 2840303, 2003; Chem. Abstr. 2004, 140, 16744.
    • (d) Taillefer, M.; Cristau, H.-J.; Cellier, P. P.; Spindler, J.-F. FR 2840303, 2003; Chem. Abstr. 2004, 140, 16744.
  • 16
    • 33846185212 scopus 로고    scopus 로고
    • The four main mechanisms proposed in the literature involve (1) oxidative addition/reductive elimination of ArX on copper(I), (2) π-complexation of ArX on copper(I), (3) Lewis-type complexation of ArX on copper(I), or (4) aryl radical intermediates. None of these mechanisms have been confirmed by experimental proofs.
    • The four main mechanisms proposed in the literature involve (1) oxidative addition/reductive elimination of ArX on copper(I), (2) π-complexation of ArX on copper(I), (3) Lewis-type complexation of ArX on copper(I), or (4) aryl radical intermediates. None of these mechanisms have been confirmed by experimental proofs.
  • 23
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    • and references cited therein
    • (g) Paine, A. J. J. Am. Chem. Soc. 1987, 109, 1496 and references cited therein.
    • (1987) J. Am. Chem. Soc , vol.109 , pp. 1496
    • Paine, A.J.1
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    • and references cited therein
    • (i) Lindley, J. Tetrahedron 1984, 40, 1433 and references cited therein.
    • (1984) Tetrahedron , vol.40 , pp. 1433
    • Lindley, J.1
  • 38
    • 16244411305 scopus 로고    scopus 로고
    • However, it is worth noting that, recently, Buchwald's works suggested that the role of (dimethylamino)cyclohexane in copper-mediated arylation of amides was to avoid formation of copper complexes containing two amidates, which are unable to promote the coupling. Note that this study only concerned the particular case of amidation reactions: Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4120.
    • However, it is worth noting that, recently, Buchwald's works suggested that the role of (dimethylamino)cyclohexane in copper-mediated arylation of amides was to avoid formation of copper complexes containing two amidates, which are unable to promote the coupling. Note that this study only concerned the particular case of amidation reactions: Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4120.
  • 41
    • 33846239702 scopus 로고    scopus 로고
    • 3-CN (see Figure 3a): at that temperature, the coupling was slower, phenyl 3,5-dimethylphenyl ether being obtained in 26% yield after 70 h (Table 1, entry 5). Better yields can be achieved by increasing the reaction time.
    • 3-CN (see Figure 3a): at that temperature, the coupling was slower, phenyl 3,5-dimethylphenyl ether being obtained in 26% yield after 70 h (Table 1, entry 5). Better yields can be achieved by increasing the reaction time.
  • 42
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    • It was, of course, the same for all of the other protons of the complexed ligand
    • It was, of course, the same for all of the other protons of the complexed ligand.
  • 44
    • 33846201780 scopus 로고    scopus 로고
    • Brooker, S.; Davidson, T. C.; Hay, S. J.; Kelly, R. J.; Kennepohl, D. K.; Plieger, P. G.; Moubakari, B.; Murray, K. S.; Bill, E.; Bothe, E. Coord. Chem. Rev. 2001, 216-217, 3. This study deals with a tetracopper(I) complex involving the octadentate ligand L. L. comprising four imine nitrogen donors and four pyridazine nitrogen donors, could thus be regarded as a dimer of our tetradentate ligand 1. According to proton NMR spectra, the structure of the tetracopper(I) complex was maintained in noncoordinating solvents such as nitromethane and acetone, whereas in acetonitrile, the latter existed in equilibrium with a dicopper(I) complex, resulting from the opening of the tetramer under the effect of the solvent.
    • Brooker, S.; Davidson, T. C.; Hay, S. J.; Kelly, R. J.; Kennepohl, D. K.; Plieger, P. G.; Moubakari, B.; Murray, K. S.; Bill, E.; Bothe, E. Coord. Chem. Rev. 2001, 216-217, 3. This study deals with a tetracopper(I) complex involving the octadentate ligand L. L. comprising four imine nitrogen donors and four pyridazine nitrogen donors, could thus be regarded as a "dimer" of our tetradentate ligand 1. According to proton NMR spectra, the structure of the tetracopper(I) complex was maintained in noncoordinating solvents such as nitromethane and acetone, whereas in acetonitrile, the latter existed in equilibrium with a dicopper(I) complex, resulting from the opening of the tetramer under the effect of the solvent.
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    • 1st ed, Wilkinson, G, Gaillard, R. D, McCleverty J. A, Eds, Pergamon Press: Oxford, U.K
    • Hathaway, B. J. In Comprehensive Coordination Chemistry, 1st ed.; Wilkinson, G., Gaillard, R. D., McCleverty J. A., Eds.; Pergamon Press: Oxford, U.K., 1987; Vol. 5, pp 536-537.
    • (1987) Comprehensive Coordination Chemistry , vol.5 , pp. 536-537
    • Hathaway, B.J.1
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    • The solubility of this complex is also very weak, even on reflux in acetonitrile
    • The solubility of this complex is also very weak, even on reflux in acetonitrile.
  • 49
    • 33846194718 scopus 로고    scopus 로고
    • Not only at 80°C but also at 40°C (monomer exclusively present, Figure 3a), the 2b-catalyzed copper arylation of 3,5-dimethylphenol with iodobenzene takes place (no reaction without ligand at 40°C) (Table 1). The yield after 24 h is, however, relatively average (26%, Table 1, entry 5), thus accounting for the low reaction temperature.
    • Not only at 80°C but also at 40°C (monomer exclusively present, Figure 3a), the 2b-catalyzed copper arylation of 3,5-dimethylphenol with iodobenzene takes place (no reaction without ligand at 40°C) (Table 1). The yield after 24 h is, however, relatively average (26%, Table 1, entry 5), thus accounting for the low reaction temperature.
  • 52
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    • Dieter, R. K.; Silks, L. A.. III; Fishpaugh, J. R.; Kastner, M. E. J. Am. Chem. Soc. 1985, 107, 4679.
    • Dieter, R. K.; Silks, L. A.. III; Fishpaugh, J. R.; Kastner, M. E. J. Am. Chem. Soc. 1985, 107, 4679.
  • 54
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    • The coexistence of monomer and dimer in the solution led to a high complexity of the signals for cyclohexane protons, thus preventing us from assigning precisely this part of the spectrum
    • The coexistence of monomer and dimer in the solution led to a high complexity of the signals for cyclohexane protons, thus preventing us from assigning precisely this part of the spectrum.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.