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Volumn 132, Issue 43, 2010, Pages 15179-15181

Efficient ring-closing metathesis of alkenyl bromides: The importance of protecting the catalyst during the olefin approach

Author keywords

[No Author keywords available]

Indexed keywords

ALKENYL; BROMOALKENE; RING CLOSING METATHESIS; RING-CLOSING METATHESIS REACTIONS;

EID: 78049403874     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja108253f     Document Type: Article
Times cited : (38)

References (41)
  • 1
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    • Wiley-VCH: Weinheim, Germany, and references therein
    • Grubbs, R. H. Handbook of Metathesis; Wiley-VCH: Weinheim, Germany, 2003, and references therein.
    • (2003) Handbook of Metathesis
    • Grubbs, R.H.1
  • 7
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    • For selected recent applications in synthesis, see
    • For selected recent applications in synthesis, see
  • 17
    • 77954243412 scopus 로고    scopus 로고
    • This paper indeed indicates that related structures to the one reported in ref 4c cannot be obtained via RCM of the corresponding alkenyl chloride substrates
    • White, D. E., Stewart, I. C., Seashore-Lodlow, B. A., Grubbs, R. H., and Stoltz, B. M. Tetrahedron 2010, 66, 4668 This paper indeed indicates that related structures to the one reported in ref 4c cannot be obtained via RCM of the corresponding alkenyl chloride substrates
    • (2010) Tetrahedron , vol.66 , pp. 4668
    • White, D.E.1    Stewart, I.C.2    Seashore-Lodlow, B.A.3    Grubbs, R.H.4    Stoltz, B.M.5
  • 18
    • 0001101871 scopus 로고    scopus 로고
    • For Grubbs II (GII), see ref 4 and b. For Schrock and Grubbs I (GI), see
    • For Grubbs II (GII), see ref 4 and b. For Schrock and Grubbs I (GI), see: Kirkland, T. A. and Grubbs, R. H. J. Org. Chem. 1997, 62, 7310
    • (1997) J. Org. Chem. , vol.62 , pp. 7310
    • Kirkland, T.A.1    Grubbs, R.H.2
  • 19
    • 78049412167 scopus 로고    scopus 로고
    • For recent efforts to use alkenyl halides in CM, see
    • For recent efforts to use alkenyl halides in CM, see
  • 22
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    • See the Supporting Information for details
    • See the Supporting Information for details.
  • 23
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    • 3 at the same concentration. See the Supporting Information for spectra
    • 3 at the same concentration. See the Supporting Information for spectra.
  • 24
    • 78049404048 scopus 로고    scopus 로고
    • To our knowledge, this is the first example where a second-generation ruthenium catalyst decomposes via formal loss of the NHC ligand. For other decomposition pathways, see
    • To our knowledge, this is the first example where a second-generation ruthenium catalyst decomposes via formal loss of the NHC ligand. For other decomposition pathways, see
  • 27
    • 34347267209 scopus 로고    scopus 로고
    • It is commonly assumed that alkenyl halides react very rapidly with the ruthenium center, giving rise to Fischer-type carbene moieties; see discussion in ref 4a and
    • It is commonly assumed that alkenyl halides react very rapidly with the ruthenium center, giving rise to Fischer-type carbene moieties; see discussion in ref 4a and: Macnaughtan, M. L., Johnson, M. J. A., and Kampf, J. W. J. Am. Chem. Soc. 2007, 129, 7708
    • (2007) J. Am. Chem. Soc. , vol.129 , pp. 7708
    • MacNaughtan, M.L.1    Johnson, M.J.A.2    Kampf, J.W.3
  • 28
    • 78049355606 scopus 로고    scopus 로고
    • In a separate experiment, we made sure that compound 2 does not react with an equimolar amount of tricyclohexylphosphine. This excludes a reaction scenario where the phosphine liberated from GII during the initial CM of 1 attacks the bromoalkene via elimination of HBr
    • In a separate experiment, we made sure that compound 2 does not react with an equimolar amount of tricyclohexylphosphine. This excludes a reaction scenario where the phosphine liberated from GII during the initial CM of 1 attacks the bromoalkene via elimination of HBr.
  • 29
    • 78049379054 scopus 로고    scopus 로고
    • Terminal substitution has been successfully used in the past to minimize unwanted secondary metathesis activity during RCM. For the first example, see
    • Terminal substitution has been successfully used in the past to minimize unwanted secondary metathesis activity during RCM. For the first example, see
  • 30
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    • For more recent, selected examples where the geometry of a terminal phenyl or methyl group affects reaction yields, see:, J. Org. Chem. 1998, 63, 9904
    • Fu, G. C. and Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324 For more recent, selected examples where the geometry of a terminal phenyl or methyl group affects reaction yields, see: Kirkland, T. A., Lynn, D. M., and Grubbs, R. H. J. Org. Chem. 1998, 63, 9904
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 7324
    • Fu, G.C.1    Grubbs, R.H.2    Kirkland, T.A.3    Lynn, D.M.4    Grubbs, R.H.5
  • 33
    • 78049399864 scopus 로고    scopus 로고
    • This strategy would also generate, after each catalytic cycle, a propagating species more stable than a methylidene. For a discussion regarding the advantages of a stable propagating species in solution, see ref 12b
    • This strategy would also generate, after each catalytic cycle, a propagating species more stable than a methylidene. For a discussion regarding the advantages of a stable propagating species in solution, see ref 12b.
  • 34
    • 78049358542 scopus 로고    scopus 로고
    • The main byproduct was unreacted starting material
    • The main byproduct was unreacted starting material.
  • 35
    • 78049412166 scopus 로고    scopus 로고
    • Screening of reaction conditions (solvents, precatalysts etc.) can be found in the Supporting Information
    • Screening of reaction conditions (solvents, precatalysts etc.) can be found in the Supporting Information.
  • 36
    • 78049370295 scopus 로고    scopus 로고
    • Reference 4d reports a 24% yield of 16a starting from the non-phenylated malonate derivative of 16 when employing 5 mol % of an optimized second-generation ruthenium precatalyst
    • Reference 4d reports a 24% yield of 16a starting from the non-phenylated malonate derivative of 16 when employing 5 mol % of an optimized second-generation ruthenium precatalyst.
  • 37
    • 0030443083 scopus 로고    scopus 로고
    • In these cases, the approach of the alkenyl bromide seems to be more difficult resulting in lower activity. For an early example on the Thorpe-Ingold effect in RCM, see
    • In these cases, the approach of the alkenyl bromide seems to be more difficult resulting in lower activity. For an early example on the Thorpe-Ingold effect in RCM, see: Fürstner, A. and Langemann, K. J. Org. Chem. 1996, 61, 8746
    • (1996) J. Org. Chem. , vol.61 , pp. 8746
    • Fürstner, A.1    Langemann, K.2
  • 38
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    • Probably, a correct and swift approach of the bromoalkene is not possible in this case. For earlier studies that show how olefin isomerization can occur before RCM, see
    • Probably, a correct and swift approach of the bromoalkene is not possible in this case. For earlier studies that show how olefin isomerization can occur before RCM, see
  • 40
    • 3943048796 scopus 로고    scopus 로고
    • references cited therein
    • Schmidt, B. Eur. J. Org. Chem. 2004, 1865 and references cited therein
    • (2004) Eur. J. Org. Chem. , pp. 1865
    • Schmidt, B.1
  • 41
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    • While compound 6 did not show any apparent reactivity, substrates 20 and 21 partially decomposed with concomitant formation of trace amounts of product (< 10%). A detailed investigation on catalyst and substrate decomposition pathways is underway
    • While compound 6 did not show any apparent reactivity, substrates 20 and 21 partially decomposed with concomitant formation of trace amounts of product (< 10%). A detailed investigation on catalyst and substrate decomposition pathways is underway.


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