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Volumn 48, Issue 32, 2009, Pages 5958-5961

Mechanistic insight into the palladium-catalyzed 1,4-oxidation of 1,3-dienes to 1,4-dicarboxy-alk-2-enes

Author keywords

Dienes; Homogeneous catalysis; Oxidation; Palladium; Reaction mechanisms

Indexed keywords

CYCLOHEXADIENES; DIASTEREO-SELECTIVITY; DIELS-ALDER ADDUCT; DIENES; HIGH RATE; HOMOGENEOUS CATALYSIS; IN-SITU; REACTION MECHANISMS; SIDE PRODUCTS;

EID: 70349902857     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200901614     Document Type: Article
Times cited : (16)

References (29)
  • 13
    • 70349911700 scopus 로고    scopus 로고
    • We increased the concentration of the reaction mixture while the maintaining the concentration of benzoic acid. The following reaction conditions were used: CHD (1 equiv, 0.32M, benzoic acid (4 equiv, 1.27 M, catalyst (1.25-5 mol, p-benzoquinone (2.2 equiv, 0.69M, acetone 30 mL per gram of CHD, room temperature. Cyclohexene and benzene are also produced during the oxidation
    • We increased the concentration of the reaction mixture while the maintaining the concentration of benzoic acid. The following reaction conditions were used: CHD (1 equiv, 0.32M), benzoic acid (4 equiv, 1.27 M), catalyst (1.25-5 mol%), p-benzoquinone (2.2 equiv, 0.69M), acetone (30 mL per gram of CHD), room temperature. Cyclohexene and benzene are also produced during the oxidation.
  • 14
    • 70349898241 scopus 로고    scopus 로고
    • 2 (Bz = benzoyl) became our preferred catalyst, as it limits the number of side products formed (no mixed-carboxylate products are produced).
    • 2 (Bz = benzoyl) became our preferred catalyst, as it limits the number of side products formed (no mixed-carboxylate products are produced).
  • 18
    • 37049054852 scopus 로고    scopus 로고
    • The deaggregation of trimeric palladium carboxylate into a monomer was ruled out as the cause of the sigmoidal profile through comparison with the use of Pd(tfa)2 (tfa, trifluoroacetate) as the catalyst, in which case a near-identical sigmoidal profile to that found with Pd(OBz)2 was observed. Pd(tfa)2 is known to be monomeric in solution: T. A. Stephenson, S. M. Morehouse, A. R. Powell, J. P. Heffer, G. Wilkinson, J. Chem. Soc. 1965, 3632
    • 2 is known to be monomeric in solution: T. A. Stephenson, S. M. Morehouse, A. R. Powell, J. P. Heffer, G. Wilkinson, J. Chem. Soc. 1965, 3632.
  • 19
    • 70349907573 scopus 로고    scopus 로고
    • Hydroquinone is the by-product of palladium(0) reoxidation and precipitates during the reaction as quinhydrone
    • Hydroquinone is the by-product of palladium(0) reoxidation and precipitates during the reaction as quinhydrone.
  • 20
    • 70349934395 scopus 로고    scopus 로고
    • 2.
    • 2.
  • 24
    • 70349900356 scopus 로고    scopus 로고
    • -1.
    • -1.
  • 27
    • 70349897319 scopus 로고    scopus 로고
    • To ensure a sufficient heat flow, the oxidation reactions were carried out at 40 °C (see the Supporting Information).
    • To ensure a sufficient heat flow, the oxidation reactions were carried out at 40 °C (see the Supporting Information).
  • 28
    • 70349915875 scopus 로고    scopus 로고
    • DZVP (DFT Orbital): N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560. Basis sets were obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 02/02/06, as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory, which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, Washington 99352, USA, and funded by the US Department of Energy. The Pacific Northwest Laboratory is operated by the Battelle Memorial Institute for the US Department of Energy under contract DE-AC06-76RLO 1830.
    • DZVP (DFT Orbital): N. Godbout, D. R. Salahub, J. Andzelm, E. Wimmer, Can. J. Chem. 1992, 70, 560. Basis sets were obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 02/02/06, as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory, which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, Washington 99352, USA, and funded by the US Department of Energy. The Pacific Northwest Laboratory is operated by the Battelle Memorial Institute for the US Department of Energy under contract DE-AC06-76RLO 1830.
  • 29
    • 70349932286 scopus 로고    scopus 로고
    • Alex A. Granovsky, PC GAMESS/Firefly version 7.1.C, www
    • Alex A. Granovsky, PC GAMESS/Firefly version 7.1.C, www http://classic.chem.msu.su/gran/gamess/index.html.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.