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Volumn 127, Issue 23, 2005, Pages 8499-8507

Using mechanistic and computational studies to explain ligand effects in the palladium-catalyzed aerobic oxidation of alcohols

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; ALCOHOLS; CATALYSIS; ISOTOPES; MATHEMATICAL MODELS; OXIDATION;

EID: 20444502894     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja050949r     Document Type: Article
Times cited : (129)

References (58)
  • 8
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    • (c) Muzart, J. Tetrahedron 2003, 59, 5789-5816.
    • (2003) Tetrahedron , vol.59 , pp. 5789-5816
    • Muzart, J.1
  • 21
    • 0034794864 scopus 로고    scopus 로고
    • For examples of Pd-catalyzed oxidative kinetic resolution, see: (a) Ferreira, E. M.; Stoltz, B. M. J. Am. Chem. Soc. 2001, 123, 7725-7726.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 7725-7726
    • Ferreira, E.M.1    Stoltz, B.M.2
  • 31
    • 20444461725 scopus 로고    scopus 로고
    • note
    • For computational studies performed on this system, see refs 7b, 8g, 8h, and 8j.
  • 34
    • 0037028556 scopus 로고    scopus 로고
    • For other mechanistic investigations on Pd-catalyzed aerobic alcohol oxidations, see: (a) Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. J. Am. Chem. Soc. 2002, 124, 766-767.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 766-767
    • Steinhoff, B.A.1    Fix, S.R.2    Stahl, S.S.3
  • 44
    • 20444437331 scopus 로고    scopus 로고
    • note
    • PhenS = bathophenanthroline disulfonate, see ref 3e.
  • 45
    • 20444448997 scopus 로고    scopus 로고
    • note
    • IiPr = 1,3-Bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazole, see ref 3h.
  • 46
    • 20444489308 scopus 로고    scopus 로고
    • note
    • Upon discovering this dependence on oxidation rate on [TEA], the alcohol dependence was measured at high [TEA] (Pd:TEA = 1:20) and saturation kinetics were observed as well.
  • 47
    • 20444491697 scopus 로고    scopus 로고
    • note
    • One possibility that cannot be ruled out in the current study is direct transfer of the hydride from the palladium alkoxide to the acetate ligand.
  • 54
    • 0003934843 scopus 로고
    • Schrödinger, Inc.: Portland, OR
    • Jaguar 4.0; Schrödinger, Inc.: Portland, OR, 1991-2000.
    • (1991) Jaguar 4.0
  • 55
    • 20444435211 scopus 로고    scopus 로고
    • note
    • Solvent effects were in general quite small, on the level of 2-4 kcal/mol for the Pd/TEA system and somewhat larger for the Pd/pyridine system.
  • 57
    • 20444500259 scopus 로고    scopus 로고
    • note
    • The use of the effective potential LanL2DZ basis set for thermochemical analysis, namely, for acquiring thermodynamic functions and Gibbs free energy, has regularly been found to result in a level of accuracy comparable to that of superior basis sets to a small fraction of computational costs.
  • 58
    • 0001532741 scopus 로고    scopus 로고
    • The pyridine has higher average Hartree-Fock local ionisation energy than the TEA ligand by almost 30 kcal/mol. Therefore Pd-TEA complexes with already electron-deficient Pd(II) should be more active than Pd-pyridine complexes in breaking of the C-H bond due to the more labile electronic density on the TEA ligand. For the computation of the average Hartree-Fock local ionization energy see: Brink, T. J. Phys. Chem. A 1997, 101, 3408-3415.
    • (1997) J. Phys. Chem. A , vol.101 , pp. 3408-3415
    • Brink, T.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.