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Volumn 5, Issue 18, 2003, Pages 3285-3288

Homeopathic ligand-free palladium as a catalyst in the heck reaction. A comparison with a palladacycle

Author keywords

[No Author keywords available]

Indexed keywords

BROMIDE; PALLADIUM;

EID: 0141856236     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035184b     Document Type: Article
Times cited : (576)

References (59)
  • 2
    • 0000633011 scopus 로고
    • Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, UK, Chapter 4.3
    • (b) Heck, R. F. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, UK, 1991; Vol 4, Chapter 4.3, p 833.
    • (1991) Comprehensive Organic Synthesis , vol.4 , pp. 833
    • Heck, R.F.1
  • 12
    • 0141804079 scopus 로고    scopus 로고
    • Ford, M. E., Ed.; Marcel Dekker Inc.: New York
    • (b) Stephan, M. S.; de Vries, J. G. In Chemical Industries 82, Catalysis of Organic Reactions; Ford, M. E., Ed.; Marcel Dekker Inc.: New York, 2000, p 379. For further work on this concept see: Goossen, L. J.; Paetzold, J.; Ghosh, K. Synlett 2002, 1721 and references therein.
    • (2000) Chemical Industries 82, Catalysis of Organic Reactions , pp. 379
    • Stephan, M.S.1    De Vries, J.G.2
  • 13
    • 84856330915 scopus 로고    scopus 로고
    • and references therein
    • (b) Stephan, M. S.; de Vries, J. G. In Chemical Industries 82, Catalysis of Organic Reactions; Ford, M. E., Ed.; Marcel Dekker Inc.: New York, 2000, p 379. For further work on this concept see: Goossen, L. J.; Paetzold, J.; Ghosh, K. Synlett 2002, 1721 and references therein.
    • (2002) Synlett , pp. 1721
    • Goossen, L.J.1    Paetzold, J.2    Ghosh, K.3
  • 14
    • 0000629440 scopus 로고    scopus 로고
    • Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT
    • Jeffery, T. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1996; Vol 5, p 153. See also: Ziegler, C. B., Jr.; Heck, R. F. J. Org. Chem. 1978, 43, 2941.
    • (1996) Advances in Metal-Organic Chemistry , vol.5 , pp. 153
    • Jeffery, T.1
  • 15
    • 33947092885 scopus 로고
    • Jeffery, T. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press: Greenwich, CT, 1996; Vol 5, p 153. See also: Ziegler, C. B., Jr.; Heck, R. F. J. Org. Chem. 1978, 43, 2941.
    • (1978) J. Org. Chem. , vol.43 , pp. 2941
    • Ziegler C.B., Jr.1    Heck, R.F.2
  • 16
    • 0141469306 scopus 로고    scopus 로고
    • note
    • The phrase "ligand-free" is used when no additional ligand, e.g., a phosphine, is added to the reaction mixture to keep the palladium in solution.
  • 20
    • 0141804080 scopus 로고    scopus 로고
    • note
    • Although aryl chlorides are cheaper than aryl bromides, the TON numbers attained for aryl chlorides are much lower than those for aryl bromides, so overall, a process based on an aryl bromide with low-loading palladium is cheaper. See also the concluding paragraph in ref 3.
  • 32
    • 0141692498 scopus 로고    scopus 로고
    • note
    • The low loading of ligand-free palladium (in our examples 0.01-0.1 mol %) has been dubbed as homeopathic doses, a phrase also used by Beletskaya and Cheprakov, see ref 1f, p 3009.
  • 34
    • 0141580946 scopus 로고    scopus 로고
    • note
    • -1.
  • 35
    • 0000740923 scopus 로고
    • A mixture of a β-trans- and β-cis-arylated product was found, see also: Andersson, C.-M.; Hallberg, A. J. Org. Chem. 1987, 52, 3529.
    • (1987) J. Org. Chem. , vol.52 , pp. 3529
    • Andersson, C.-M.1    Hallberg, A.2
  • 39
    • 0141469305 scopus 로고    scopus 로고
    • note
    • The observed TOF values for the palladacycle in NMP correspond nicely with the ones reported in DMF, see ref 22.
  • 49
    • 0035820028 scopus 로고    scopus 로고
    • Pfaltz and Blackmond, in their study on the kinetics of a Heck reaction catalyzed by a palladacycle, assumed that this phenomenon is due to a preequilibrium between a dimeric and a monomeric aryl-Pd(II) species. They found half-order in [Pd]. See: Rosner, T.; Le Bars, J.; Pfaltz, A.; Blackmond, D. G. J. Am. Chem. Soc. 2001, 123, 1848. For the cluster case an order between 0 and 1 is expected.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 1848
    • Rosner, T.1    Le Bars, J.2    Pfaltz, A.3    Blackmond, D.G.4
  • 52
    • 0141630304 scopus 로고    scopus 로고
    • The actual mechanism is currently a subject of study. Very recently a palladacycle was proposed as a reservoir of an active Pd(0) species, see: Consorti, C. S.; Zanini, M. L.; Leal, S.; Ebeling, G.; Dupont, J. Org. Lett. 2003, 5, 983.
    • (2003) Org. Lett. , vol.5 , pp. 983
    • Consorti, C.S.1    Zanini, M.L.2    Leal, S.3    Ebeling, G.4    Dupont, J.5


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.