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Volumn 42, Issue 31, 2003, Pages 3674-3677

Quinox, a quinoline-type N-oxide, as organocatalyst in the asymmetric allylation of aromatic aldehydes with allyltrichlorosilanes: The role of arene-arene interactions

Author keywords

Allylation; Arenes; Asymmetric catalysis; O ligands; Organocatalysis

Indexed keywords

CATALYSTS; ELECTRONS; SILANES;

EID: 0041967639     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351737     Document Type: Article
Times cited : (190)

References (41)
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    • For a recent account on the face-to-face and center-to-edge interactions on aromatic systems and polar effects, see: a) F. Cozzi, R. Annunziata, M. Benaglia, M. Cinquini, L. Raimondi, K. K. Baldridge, J. S. Siegel, Org. Biomol. Chem. 2003, 1, 157; b) For a recent review on the arene-arene, π stacking, and C-H/ π interactions, see: E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. 2003, 115, 1244; Angew. Chem. Int. Ed. 2003, 42, 1210; c) For C-H/π interactions, see: P. Hobza, Z. Havlas, Chem. Rev. 2000, 100, 4253; d) For a review on π shielding in organic synthesis, see: G. B. Jones, Tetrahedron 2001, 57, 7999.
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    • Cozzi, F.1    Annunziata, R.2    Benaglia, M.3    Cinquini, M.4    Raimondi, L.5    Baldridge, K.K.6    Siegel, J.S.7
  • 22
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    • For a recent account on the face-to-face and center-to-edge interactions on aromatic systems and polar effects, see: a) F. Cozzi, R. Annunziata, M. Benaglia, M. Cinquini, L. Raimondi, K. K. Baldridge, J. S. Siegel, Org. Biomol. Chem. 2003, 1, 157; b) For a recent review on the arene-arene, π stacking, and C-H/ π interactions, see: E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. 2003, 115, 1244; Angew. Chem. Int. Ed. 2003, 42, 1210; c) For C-H/π interactions, see: P. Hobza, Z. Havlas, Chem. Rev. 2000, 100, 4253; d) For a review on π shielding in organic synthesis, see: G. B. Jones, Tetrahedron 2001, 57, 7999.
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    • Meyer, E.A.1    Castellano, R.K.2    Diederich, F.3
  • 23
    • 0242417008 scopus 로고    scopus 로고
    • For a recent account on the face-to-face and center-to-edge interactions on aromatic systems and polar effects, see: a) F. Cozzi, R. Annunziata, M. Benaglia, M. Cinquini, L. Raimondi, K. K. Baldridge, J. S. Siegel, Org. Biomol. Chem. 2003, 1, 157; b) For a recent review on the arene-arene, π stacking, and C-H/ π interactions, see: E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. 2003, 115, 1244; Angew. Chem. Int. Ed. 2003, 42, 1210; c) For C-H/π interactions, see: P. Hobza, Z. Havlas, Chem. Rev. 2000, 100, 4253; d) For a review on π shielding in organic synthesis, see: G. B. Jones, Tetrahedron 2001, 57, 7999.
    • (2003) Angew. Chem. Int. Ed. , vol.42 , pp. 1210
  • 24
    • 0034317323 scopus 로고    scopus 로고
    • For a recent account on the face-to-face and center-to-edge interactions on aromatic systems and polar effects, see: a) F. Cozzi, R. Annunziata, M. Benaglia, M. Cinquini, L. Raimondi, K. K. Baldridge, J. S. Siegel, Org. Biomol. Chem. 2003, 1, 157; b) For a recent review on the arene-arene, π stacking, and C-H/ π interactions, see: E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. 2003, 115, 1244; Angew. Chem. Int. Ed. 2003, 42, 1210; c) For C-H/π interactions, see: P. Hobza, Z. Havlas, Chem. Rev. 2000, 100, 4253; d) For a review on π shielding in organic synthesis, see: G. B. Jones, Tetrahedron 2001, 57, 7999.
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    • For a recent account on the face-to-face and center-to-edge interactions on aromatic systems and polar effects, see: a) F. Cozzi, R. Annunziata, M. Benaglia, M. Cinquini, L. Raimondi, K. K. Baldridge, J. S. Siegel, Org. Biomol. Chem. 2003, 1, 157; b) For a recent review on the arene-arene, π stacking, and C-H/ π interactions, see: E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. 2003, 115, 1244; Angew. Chem. Int. Ed. 2003, 42, 1210; c) For C-H/π interactions, see: P. Hobza, Z. Havlas, Chem. Rev. 2000, 100, 4253; d) For a review on π shielding in organic synthesis, see: G. B. Jones, Tetrahedron 2001, 57, 7999.
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    • Jones, G.B.1
  • 26
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    • note
    • The π stacking has also been proposed by Hayashi to account for the high catalytic activity of a chiral 2,2′-bipyridine-N,N-bisoxide.[4]
  • 30
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    • note
    • For the previous use of binol to resolve bipyridine-type N,N-bisoxides, see refs [3,4].
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    • note
    • While this work was in progress, Nakajima published the same synthesis of (+)-11, including the resolution with -(-)-binol.[3d] However, this synthesis was mentioned as a footnote without specifying the conditions and the absolute configuration of (+)-11 was not determined.
  • 32
    • 0042027015 scopus 로고    scopus 로고
    • note
    • F(obs) = 0.0395.
  • 33
    • 0042527848 scopus 로고    scopus 로고
    • note
    • Investigation of the allylation of 1a with 2, catalyzed by -(+)-11 of 29%, 50%, and 75% ee, respectively, has demonstrated a fully linear relationship between the enantiopurity of the catalyst and the product. In these experiments, the resulting product 3a was of 27%, 45%, and 71% ee, respectively.
  • 34
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    • Chloroform has been shown to be the solvent that most strongly stabilizes the arene-arene interactions: G. A. Breault, C. A. Hunter, P. C. Mayers, J. Am. Chem. Soc. 1998, 120, 3402.
    • (1998) J. Am. Chem. Soc. , vol.120 , pp. 3402
    • Breault, G.A.1    Hunter, C.A.2    Mayers, P.C.3
  • 39
    • 0000009579 scopus 로고
    • For a discussion on cyclic/open transition state, see: a) S. E. Denmark, N. G. Almstead, J. Org. Chem. 1994, 59, 5130; b) S. E. Denmark, S. Hosoi, J. Org. Chem. 1994, 59, 5133.
    • (1994) J. Org. Chem. , vol.59 , pp. 5130
    • Denmark, S.E.1    Almstead, N.G.2
  • 40
    • 0000032965 scopus 로고
    • For a discussion on cyclic/open transition state, see: a) S. E. Denmark, N. G. Almstead, J. Org. Chem. 1994, 59, 5130; b) S. E. Denmark, S. Hosoi, J. Org. Chem. 1994, 59, 5133.
    • (1994) J. Org. Chem. , vol.59 , pp. 5133
    • Denmark, S.E.1    Hosoi, S.2
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    • note
    • Hayashi has proposed π-π stacking of 1 and the catalysts but, in his case, the variation of the enantioselectivity was less dramatic (94% ee for 1d and 56% ee for 1l as the extremes of the scale).[4] Furthermore, his catalyst gave the best results in MeCN, which is known not to support arene-arene interactions,[15] thus suggesting that his and our catalyst may operate through a different mode of interactions.


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