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a) J.-E. Bäckvall, J. E. Nystroem, R. E. Nordberg, J. Am. Chem. Soc. 1985, 107, 3676;
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70349911700
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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
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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.
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70349898241
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2 (Bz = benzoyl) became our preferred catalyst, as it limits the number of side products formed (no mixed-carboxylate products are produced).
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2 (Bz = benzoyl) became our preferred catalyst, as it limits the number of side products formed (no mixed-carboxylate products are produced).
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37049054852
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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
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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.
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Hydroquinone is the by-product of palladium(0) reoxidation and precipitates during the reaction as quinhydrone
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Hydroquinone is the by-product of palladium(0) reoxidation and precipitates during the reaction as quinhydrone.
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70349934395
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21344470856
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Grundl, M.A.1
Kennedy-Smith, J.J.2
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0000212666
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b) S. Porth, J. W. Bats, D. Trauner, G. Giester, J. Mulzer, Angew. Chem. 1999, 111, 2159;
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Porth, S.1
Bats, J.W.2
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a) A. C. Ferretti, J. S. Mathew, D. G. Blackmond, Ind. Eng. Chem. Res. 2007, 46, 8584;
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Ferretti, A.C.1
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b) J. S. Mathew, M. Klussmann, H. Iwamura, F. Valera, A. Futran, E. Alan, E. A. C. Emanuelsson, D. G. Blackmond, J. Org. Chem. 2006, 71, 4711.
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Mathew, J.S.1
Klussmann, M.2
Iwamura, H.3
Valera, F.4
Futran, A.5
Alan, E.6
Emanuelsson, E.A.C.7
Blackmond, D.G.8
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70349897319
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To ensure a sufficient heat flow, the oxidation reactions were carried out at 40 °C (see the Supporting Information).
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To ensure a sufficient heat flow, the oxidation reactions were carried out at 40 °C (see the Supporting Information).
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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.
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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.
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Alex A. Granovsky, PC GAMESS/Firefly version 7.1.C, www
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Alex A. Granovsky, PC GAMESS/Firefly version 7.1.C, www http://classic.chem.msu.su/gran/gamess/index.html.
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