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Volumn 130, Issue 30, 2008, Pages 9971-9983

Copper complexes of anionic nitrogen ligands in the amidation and imidation of aryl halides

Author keywords

[No Author keywords available]

Indexed keywords

AMIDATE; AMIDATION; ANIONIC NITROGEN; ARYL HALIDES; COPPER (II) COMPLEXES; COPPER(I); IMIDATION; N DONOR LIGANDS; PLANAR STRUCTURES; SOLID STATES; SOLUTION PHASE METHODS; X RAY DIFFRACTION (XRD);

EID: 48249117090     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja076668w     Document Type: Article
Times cited : (289)

References (75)
  • 2
    • 0004136578 scopus 로고    scopus 로고
    • Ricci, A, Ed, Wiley-VCH: Weinheim, Germany
    • Hartwig, J. F. In Modern Amination Methods; Ricci, A., Ed.; Wiley-VCH: Weinheim, Germany, 2000.
    • (2000) Modern Amination Methods
    • Hartwig, J.F.1
  • 30
    • 48249125923 scopus 로고    scopus 로고
    • For a related synthesis, see ref 26
    • For a related synthesis, see ref 26.
  • 37
    • 48249121256 scopus 로고    scopus 로고
    • 7 at -25°C contained resonances at 3.19 and 1.84 ppm in a 2:4 ratio for the six protons of the pyrr ligand.
    • 7 at -25°C contained resonances at 3.19 and 1.84 ppm in a 2:4 ratio for the six protons of the pyrr ligand.
  • 39
    • 48249095098 scopus 로고    scopus 로고
    • Reactions with other reagents that would be present in the catalytic reaction were also investigated. The addition of 9 equiv of pyrrolidinone or 19 equiv of K3PO4 formed the two products in ratios of 72:28 and 77:23, respectively
    • 4 formed the two products in ratios of 72:28 and 77:23, respectively.
  • 57
    • 48249089381 scopus 로고    scopus 로고
    • More recent measurements of the bromide dissociation from bromonaphthalene radical anions by pulse radiolysis showed the absolute rate constants to be larger than those reported in previous studies see ref 43, However, the value for dissociation of chloride was not remeasured, and it is likely to also increase in value because the assessment of smaller values resulted from technique, not the chemistry of these haloarene radical anions
    • More recent measurements of the bromide dissociation from bromonaphthalene radical anions by pulse radiolysis showed the absolute rate constants to be larger than those reported in previous studies (see ref 43). However, the value for dissociation of chloride was not remeasured, and it is likely to also increase in value because the assessment of smaller values resulted from technique, not the chemistry of these haloarene radical anions.
  • 58
    • 48249086647 scopus 로고    scopus 로고
    • It was difficult to monitor the conversion of the copper complex due to the accumulation of paramagnetic materials during the reaction. However, this reaction formed 38% of the N-aryl product after 7 h. Thus, the yield after 2 h reflects nearly full conversion of the copper
    • It was difficult to monitor the conversion of the copper complex due to the accumulation of paramagnetic materials during the reaction. However, this reaction formed 38% of the N-aryl product after 7 h. Thus, the yield after 2 h reflects nearly full conversion of the copper.
  • 61
    • 48249102017 scopus 로고    scopus 로고
    • All calculations were carried out with the Gaussian 03 program: Frisch, M. J.; et al. Gaussian 03, revision C.02; Gaussian Inc.: Wallingford, CT, 2004 See Supporting Information for the full reference.
    • All calculations were carried out with the Gaussian 03 program: Frisch, M. J.; et al. Gaussian 03, revision C.02; Gaussian Inc.: Wallingford, CT, 2004 See Supporting Information for the full reference.
  • 62
    • 48249147082 scopus 로고    scopus 로고
    • Alternatively, a lower energy pathway to the Cu(III) species could involve an intimate electron-transfer process prior to formation of the Cu(III) species without generation of a free aryl halide radical anion or aryl radical. Calculations of mechanisms involving diradical intermediates are challenging, and we have not been able to optimize either singlet or triplet structures in which an unpaired electron is located on the iodoarene
    • Alternatively, a lower energy pathway to the Cu(III) species could involve an intimate electron-transfer process prior to formation of the Cu(III) species without generation of a free aryl halide radical anion or aryl radical. Calculations of mechanisms involving diradical intermediates are challenging, and we have not been able to optimize either singlet or triplet structures in which an unpaired electron is located on the iodoarene.
  • 65
    • 48249091386 scopus 로고    scopus 로고
    • 2 to generate copper(0).
    • 2 to generate copper(0).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.