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Volumn 4, Issue 6, 1998, Pages 1083-1089

Mechanism of palladium-catalyzed allylic acetoxylation of cyclohexene

Author keywords

Allylic oxidation; Homogeneous catalysis; Isotopic labeling; Palladium; Pi allyl intermediates

Indexed keywords


EID: 2642699934     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3765(19980615)4:6<1083::aid-chem1083>3.0.co;2-f     Document Type: Article
Times cited : (73)

References (79)
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    • b) For recent enantioselective applications see: A. S. Gokhale, A. B. E. Minidis, A. Pfaltz, Tetrahedron Lett. 1995, 36, 1831; M. N. Andrus, A. B. Argade, X. Chen, M. G. Pamment, ibid. 1995, 36, 2945; C. Zondervan, B. L. Feringa, Tetrahedron Asymmetry 1996, 7, 1898; A. D. Gupta, V. K. Sing, Tetrahedron Lett. 1996, 37, 2633; M. J. Södergren, P. G. Andersson, ibid. 1996, 37, 7577.
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    • b) For recent enantioselective applications see: A. S. Gokhale, A. B. E. Minidis, A. Pfaltz, Tetrahedron Lett. 1995, 36, 1831; M. N. Andrus, A. B. Argade, X. Chen, M. G. Pamment, ibid. 1995, 36, 2945; C. Zondervan, B. L. Feringa, Tetrahedron Asymmetry 1996, 7, 1898; A. D. Gupta, V. K. Sing, Tetrahedron Lett. 1996, 37, 2633; M. J. Södergren, P. G. Andersson, ibid. 1996, 37, 7577.
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    • b) For recent enantioselective applications see: A. S. Gokhale, A. B. E. Minidis, A. Pfaltz, Tetrahedron Lett. 1995, 36, 1831; M. N. Andrus, A. B. Argade, X. Chen, M. G. Pamment, ibid. 1995, 36, 2945; C. Zondervan, B. L. Feringa, Tetrahedron Asymmetry 1996, 7, 1898; A. D. Gupta, V. K. Sing, Tetrahedron Lett. 1996, 37, 2633; M. J. Södergren, P. G. Andersson, ibid. 1996, 37, 7577.
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    • b) For recent enantioselective applications see: A. S. Gokhale, A. B. E. Minidis, A. Pfaltz, Tetrahedron Lett. 1995, 36, 1831; M. N. Andrus, A. B. Argade, X. Chen, M. G. Pamment, ibid. 1995, 36, 2945; C. Zondervan, B. L. Feringa, Tetrahedron Asymmetry 1996, 7, 1898; A. D. Gupta, V. K. Sing, Tetrahedron Lett. 1996, 37, 2633; M. J. Södergren, P. G. Andersson, ibid. 1996, 37, 7577.
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    • An extension to allow carboxylate nucleophiles other than acetate has further increased the utility of the reaction. See: B. Äkermark, E. M. Larsson, J. D. Oslob, J. Org. Chem. 1994, 59, 5729.
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    • For example: a) R. G. Brown, R. V. Chaudhar, J. M. Davidsson, J. Chem. Soc. Dalton Trans. 1977, 176; b) B. M. Trost, P. J. Metzner, J. Am. Chem. Soc. 1980, 102, 3572; J. E. Bäckvall, K. Zetterberg, B. Åkermark, in Inorganic Reactions and Methods (Ed.: A. P. Hagen), VCH. Weinheim 1991, Vol. 12A, pp. 123; D. R. Chrisope, P. Beak, W. H. Saunders, J. Am. Chem. Soc. 1988, 110, 230.
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    • Ed.: A. P. Hagen, VCH. Weinheim
    • For example: a) R. G. Brown, R. V. Chaudhar, J. M. Davidsson, J. Chem. Soc. Dalton Trans. 1977, 176; b) B. M. Trost, P. J. Metzner, J. Am. Chem. Soc. 1980, 102, 3572; J. E. Bäckvall, K. Zetterberg, B. Åkermark, in Inorganic Reactions and Methods (Ed.: A. P. Hagen), VCH. Weinheim 1991, Vol. 12A, pp. 123; D. R. Chrisope, P. Beak, W. H. Saunders, J. Am. Chem. Soc. 1988, 110, 230.
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    • For example: a) R. G. Brown, R. V. Chaudhar, J. M. Davidsson, J. Chem. Soc. Dalton Trans. 1977, 176; b) B. M. Trost, P. J. Metzner, J. Am. Chem. Soc. 1980, 102, 3572; J. E. Bäckvall, K. Zetterberg, B. Åkermark, in Inorganic Reactions and Methods (Ed.: A. P. Hagen), VCH. Weinheim 1991, Vol. 12A, pp. 123; D. R. Chrisope, P. Beak, W. H. Saunders, J. Am. Chem. Soc. 1988, 110, 230.
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    • This is of importance since a (π-allyl) intermediate would yield allylic acetates from the attack of the acetate nucleophile at Cl and C3, whereas in acetoxypalladation the acetoxylation occurs at Cl and C2 (see Scheme 2)
    • This is of importance since a (π-allyl) intermediate would yield allylic acetates from the attack of the acetate nucleophile at Cl and C3, whereas in acetoxypalladation the acetoxylation occurs at Cl and C2 (see Scheme 2).
  • 49
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    • See refs [5-10]
    • a) See refs [5-10];
  • 50
    • 2642613843 scopus 로고    scopus 로고
    • unpublished results from our laboratory
    • b) H. Grennberg, unpublished results from our laboratory.
    • Grennberg, H.1
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    • 1H NMR spectroscopy
    • 1H NMR spectroscopy.
  • 55
    • 2642706040 scopus 로고    scopus 로고
    • See the Experimental Section
    • See the Experimental Section.
  • 56
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    • A 1:1 mixture of allylic acetate (2 and 3) and bis-allylic diacetate (15 and 16) was obtained
    • A 1:1 mixture of allylic acetate (2 and 3) and bis-allylic diacetate (15 and 16) was obtained.
  • 57
    • 2642614719 scopus 로고    scopus 로고
    • With this oxidation system, numerous additional products were observed by capillary GLC. No attempt at isolation or identification of these side-products was made
    • With this oxidation system, numerous additional products were observed by capillary GLC. No attempt at isolation or identification of these side-products was made.
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    • 2642673765 scopus 로고    scopus 로고
    • suggested that a chloro complex reacts by different reaction pathways than does the corresponding acetato complex. See ref. [14b]
    • Wolfe et al. suggested that a chloro complex reacts by different reaction pathways than does the corresponding acetato complex. See ref. [14b].
    • Wolfe1
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    • For example: a) L. E. Overman, F. M. Knoll. Tetrahedron Lett. 1979, 321; b) J. Clayden, E. W. Collington, S. Warren, ibid, 1992, 33, 7039; P. M. Henry, J. Am. Chem. Soc. 1972, 94, 5200; L. E. Overman, Angew. Chem. 1984, 96, 565; Angew. Chem. Int. Ed. Engt. 1984, 23, 579.
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    • For example: a) L. E. Overman, F. M. Knoll. Tetrahedron Lett. 1979, 321; b) J. Clayden, E. W. Collington, S. Warren, ibid, 1992, 33, 7039; P. M. Henry, J. Am. Chem. Soc. 1972, 94, 5200; L. E. Overman, Angew. Chem. 1984, 96, 565; Angew. Chem. Int. Ed. Engt. 1984, 23, 579.
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    • For example: a) L. E. Overman, F. M. Knoll. Tetrahedron Lett. 1979, 321; b) J. Clayden, E. W. Collington, S. Warren, ibid, 1992, 33, 7039; P. M. Henry, J. Am. Chem. Soc. 1972, 94, 5200; L. E. Overman, Angew. Chem. 1984, 96, 565; Angew. Chem. Int. Ed. Engt. 1984, 23, 579.
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    • For example: a) L. E. Overman, F. M. Knoll. Tetrahedron Lett. 1979, 321; b) J. Clayden, E. W. Collington, S. Warren, ibid, 1992, 33, 7039; P. M. Henry, J. Am. Chem. Soc. 1972, 94, 5200; L. E. Overman, Angew. Chem. 1984, 96, 565; Angew. Chem. Int. Ed. Engt. 1984, 23, 579.
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    • For example: a) L. E. Overman, F. M. Knoll. Tetrahedron Lett. 1979, 321; b) J. Clayden, E. W. Collington, S. Warren, ibid, 1992, 33, 7039; P. M. Henry, J. Am. Chem. Soc. 1972, 94, 5200; L. E. Overman, Angew. Chem. 1984, 96, 565; Angew. Chem. Int. Ed. Engt. 1984, 23, 579.
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    • 2 (see ref. [14a])
    • 2 (see ref. [14a]).
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    • note
    • II (see ref. [28]).
  • 72
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    • Such rearrangements with a number of metal catalysts have been discussed. See for example: a) G. W. Parshall, S. D. Ittel, in Homo genons Catalysis; the Application and Chemistry of Catalysis by Soluble Transistion Metals. 2nd ed, Wiley Intcrscience, NY 1992, pp.14; b) H. G. Tange, D. G. Sherrington, J. Mol Catal. 1994, 94, 7.
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    • Tange, H.G.1    Sherrington, D.G.2
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    • 1H NMR integrals of H1, H2, and H3 has a value less than that expected from the amount of deuterium in the substrate
    • 1H NMR integrals of H1, H2, and H3 has a value less than that expected from the amount of deuterium in the substrate.
  • 75
    • 2642607194 scopus 로고    scopus 로고
    • The results do not suggest the involvement of an acetoxypalladation
    • The results do not suggest the involvement of an acetoxypalladation.
  • 77
    • 2642674602 scopus 로고    scopus 로고
    • note
    • Under these conditions, that is in the presence of strong acid, a control experiment with 7 showed that some isomerization to 8 by an 1,3- allylic transposition occurs parallel to the rearrangement of allylic to homoallylic acetate. Therefore, the labeling experiments under these conditions can not be used as strong evidence for the (π-allyl) pathway.
  • 78
    • 2642642299 scopus 로고    scopus 로고
    • Minor formation of 1,4-diacetate 12 was observed
    • Minor formation of 1,4-diacetate 12 was observed.


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