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Volumn 24, Issue 2, 2005, Pages 287-301

Development, scope, and mechanism of the palladium-catalyzed intramolecular hydroalkylation of 3-butenyl β-diketones

Author keywords

[No Author keywords available]

Indexed keywords

CHAIN TRANSFER; LEWIS ACID; NUCLEOPHILES; PROTONOLYSIS;

EID: 12844278713     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om049373p     Document Type: Article
Times cited : (35)

References (141)
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    • 20c has also been reported. (b) Rönn, M.; Andersson, G. G.; Bäckvall, J. E. Tetrahedron Lett. 1997, 38, 3603. (c) Dorange, I.; Löfstedt, J.; Närhi, K.; Franzén, J.; Bäckvall, J. E. Chem. Eur. J. 2003, 9, 3445.
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    • 20c has also been reported. (b) Rönn, M.; Andersson, G. G.; Bäckvall, J. E. Tetrahedron Lett. 1997, 38, 3603. (c) Dorange, I.; Löfstedt, J.; Närhi, K.; Franzén, J.; Bäckvall, J. E. Chem. Eur. J. 2003, 9, 3445.
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    • note
    • 28 of unactivated olefins have also been reported.
  • 74
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    • A portion of these results have been communicated: (a) Pei, T.; Widenhoefer, R. A. J. Am. Chem. Soc. 2001, 123, 11290. (b) Qian, H.; Widenhoefer, R. A. J. Am. Chem. Soc. 2003, 125, 2056.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 11290
    • Pei, T.1    Widenhoefer, R.A.2
  • 75
    • 0037467052 scopus 로고    scopus 로고
    • A portion of these results have been communicated: (a) Pei, T.; Widenhoefer, R. A. J. Am. Chem. Soc. 2001, 123, 11290. (b) Qian, H.; Widenhoefer, R. A. J. Am. Chem. Soc. 2003, 125, 2056.
    • (2003) J. Am. Chem. Soc. , vol.125 , pp. 2056
    • Qian, H.1    Widenhoefer, R.A.2
  • 85
    • 12844260689 scopus 로고    scopus 로고
    • note
    • The major competing reaction pathway in die palladium-catalyzed cyclization of 3-butenyl β-keto estera was olefin isomeriiation to form 3-oxo-5-heptenoates.
  • 100
    • 12844284503 scopus 로고    scopus 로고
    • note
    • 2.
  • 105
    • 12844276501 scopus 로고    scopus 로고
    • note
    • 8 solution of 4 (11 mM) displayed a 1:1.3 ratio of singlets at ó 2.35 and 1.95 corresponding to methyl group of coordinated and free acetonitrile, respectively.
  • 106
    • 12844258072 scopus 로고    scopus 로고
    • note
    • + in the presence of 4 points to irreversible binding of the enolate to palladium, presumably via displacement of a chloride ligand.
  • 107
    • 12844262789 scopus 로고    scopus 로고
    • note
    • tot) refers to the sum of free and coordinated acetonitrile.
  • 116
    • 12844260081 scopus 로고    scopus 로고
    • note
    • 62b the predominant formation of 2-acyl-1-hydroxy-1,3- hexadiene (7-enol) relative to 2-acyl-2-cyclohexenone (7-keto) strongly suggests that 7-enol is formed as the kinetic product in these transformations.
  • 118
    • 12844276502 scopus 로고    scopus 로고
    • note
    • 3CN. The extreme insolubility of 16 in dioxane mandated the use of acetonitrile in this experiment. Unfortunately, this precludes direct comparison of the rate of protonolysis of 16 under stoichiometric conditions to the rate of protonolysis of 16 under catalytically relevant conditions.
  • 123
    • 12844278611 scopus 로고    scopus 로고
    • note
    • 57
  • 130
    • 12844280469 scopus 로고    scopus 로고
    • note
    • The only organic byproduct not accounted for by this mechanism is phenol 15, which is presumably generated in a separate reaction manifold via oxidation of dienol 14. The stability of 5 under reaction conditions rules out formation of 14 or 15 via secondary oxidation of 5.
  • 131
    • 0001302539 scopus 로고
    • Olefin displacement from square-planar Pd(II) complexes is, with rare exceptions, strictly associative, (a) Howell, J. A. S.; Burkinshaw, P. M. Chem. Rev. 1983, 83, 557. (b) Darensbourg, D. J. Adv. Organomet. Chem. 1982, 21, 113.
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    • Howell, J.A.S.1    Burkinshaw, P.M.2
  • 132
    • 0000809685 scopus 로고
    • Olefin displacement from square-planar Pd(II) complexes is, with rare exceptions, strictly associative, (a) Howell, J. A. S.; Burkinshaw, P. M. Chem. Rev. 1983, 83, 557. (b) Darensbourg, D. J. Adv. Organomet. Chem. 1982, 21, 113.
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    • Darensbourg, D.J.1
  • 138
    • 12844281061 scopus 로고    scopus 로고
    • note
    • 3CN) intermediate with 3 is also in full accord with our observations.
  • 139
    • 12844268050 scopus 로고    scopus 로고
    • note
    • 1/2 ≈50 min) under these conditions (Figure S1).


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