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Volumn 9, Issue 1, 2003, Pages 96-105

The final steps of the oppolzer cyclization: Mechanism of the insertion of alkenes into allylpalladium(II) complexes

Author keywords

Allylation; Carbocycles; Density functional calculations; Insertion; Palladium

Indexed keywords

COMPUTATIONAL METHODS; OLEFINS; PALLADIUM;

EID: 0142067982     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200390035     Document Type: Article
Times cited : (19)

References (72)
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    • a) W. Oppolzer, in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991. Chapter 1.2;
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    • (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, Chapter 8.3
    • b) W. Oppolzer, in Comprehensive Organometallic Chemistry 11, Vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, Chapter 8.3;
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    • c) W. Oppolzer, Angew. Chem. 1989, 101, 39-53; Angew. Chem. Int. Ed. Engl. 1989, 28, 38-52;
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    • 1-allyl)palladium(11) complexes have been shown to react with alkenes to yield 3+2 cycloadducts instead of insertion derivatives: H. Kurosawa, A. Urabe, K. Miki, N. Kasai, Organo-metallics 1986, 5, 2002-2008, and references cited therein.
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    • note
    • 3 (20 mol %), toluene under reflux, 16 h afforded selectively 4b in 95 % yield.
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    • 3-allyl)palladium complexes may be involved in the palladium-catalyzed benzannulation of alkynes with allyl tosylates: N. Tsukada, S. Sugawara, Y. Inoue, Org. Lett. 2000, 2, 655-657.
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    • In palladium complexes with the allyl and alkenyl tethered by a chain, the planar or perpendicular arrangements might be controlled by conformational constraints. Thus, both arrangements have been found in solution and in the solid state for a cationic complex of this type: M. E. Kraft, M. Sugiura, K. A. Aboud, J. Am. Chem. Soc. 2001, 123, 9174-9175. See also: R. Ciajolo, M. A. Jama, A. Tuzi, A. Vitagliano, J. Organomet. Chem. 1985, 295, 233-238.
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    • In palladium complexes with the allyl and alkenyl tethered by a chain, the planar or perpendicular arrangements might be controlled by conformational constraints. Thus, both arrangements have been found in solution and in the solid state for a cationic complex of this type: M. E. Kraft, M. Sugiura, K. A. Aboud, J. Am. Chem. Soc. 2001, 123, 9174-9175. See also: R. Ciajolo, M. A. Jama, A. Tuzi, A. Vitagliano, J. Organomet. Chem. 1985, 295, 233-238.
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  • 60
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    • 3, the π contribution has been estimated to represent 25% of the σ-donor contribution: a) Ó. González-Blanco, V. Brachandell, Organometallics 1997, 16, 5556-5562; b) D. Woska, A. Prock, W. P. Giering, Organometallics 2000, 19, 4629-4638.
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  • 61
    • 0034292729 scopus 로고    scopus 로고
    • 3, the π contribution has been estimated to represent 25% of the σ-donor contribution: a) Ó. González-Blanco, V. Brachandell, Organometallics 1997, 16, 5556-5562; b) D. Woska, A. Prock, W. P. Giering, Organometallics 2000, 19, 4629-4638.
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    • Woska, D.1    Prock, A.2    Giering, W.P.3
  • 63
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    • Complex Xd has been previously studied: a) K. J. Szabó, Organometallics 1996, 15, 1128-1133; b) S. Sakaki, K. Takeuchi, M. Sugimoto, Organometallics 1997, 16, 2995-3003.
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  • 64
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    • Complex Xd has been previously studied: a) K. J. Szabó, Organometallics 1996, 15, 1128-1133; b) S. Sakaki, K. Takeuchi, M. Sugimoto, Organometallics 1997, 16, 2995-3003.
    • (1997) Organometallics , vol.16 , pp. 2995-3003
    • Sakaki, S.1    Takeuchi, K.2    Sugimoto, M.3
  • 66
    • 0346221814 scopus 로고    scopus 로고
    • note
    • Other usual solvents for these reactions have similar dielectric constants (toluene 2.38, and acetic acid 6.15).
  • 67
    • 0346852365 scopus 로고    scopus 로고
    • note
    • -1).
  • 69
    • 0347482890 scopus 로고    scopus 로고
    • note
    • [32] However, this protocol proved to be less satisfactory than the two-step procedure used in our work.
  • 71
    • 0346852364 scopus 로고    scopus 로고
    • note
    • An intramolecular Pd-catalyzed Oppolzer reaction provided a mixture of 7a and its trans isomer 7b, thus allowing for the NMR determination of any 7b that could have been formed from 7a. Pure 7b has been obtained by an intramolecular Pd-catalyzed coupling;


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