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Volumn 47, Issue 16, 2008, Pages 2982-2985

Helical (5Z, 11E)-dibenzo[a,e]cyclooctatetrene: A spring-loaded monomer

Author keywords

Catalysis; Nanotechnology; Olefin metathesis; Polycycles; Polymers

Indexed keywords

MONOMERS; OLEFINS;

EID: 53549100449     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200704355     Document Type: Article
Times cited : (21)

References (41)
  • 8
    • 33846235494 scopus 로고    scopus 로고
    • For a general discussion of these types of molecules see
    • For a general discussion of these types of molecules see: R. Herges, Chem. Rev. 2006, 106, 4820-4842.
    • (2006) Chem. Rev , vol.106 , pp. 4820-4842
    • Herges, R.1
  • 9
    • 53549127462 scopus 로고    scopus 로고
    • The experimental details for the synthesis of 3 are contained in the Supporting Information.
    • The experimental details for the synthesis of 3 are contained in the Supporting Information.
  • 10
    • 0011985659 scopus 로고    scopus 로고
    • This is approximately 3 kcal mol-1 lower than 2. In general, the benzannulated forms of such conjugated cycles are more stable than their unsubstituted forms; see for example: F. Sondheimer, Acc. Chem. Res. 1972, 5, 81-91
    • -1 lower than 2. In general, the benzannulated forms of such conjugated cycles are more stable than their unsubstituted forms; see for example: F. Sondheimer, Acc. Chem. Res. 1972, 5, 81-91.
  • 11
    • 1542744425 scopus 로고    scopus 로고
    • Substituted versions of 2 have been invoked as intermediates and transient photoproducts, see: a E. H. White, E. W. Friend, R. L. Stern, H. Maskill, J. Am. Chem. Soc. 1969, 91, 523-525;
    • Substituted versions of 2 have been invoked as intermediates and transient photoproducts, see: a) E. H. White, E. W. Friend, R. L. Stern, H. Maskill, J. Am. Chem. Soc. 1969, 91, 523-525;
  • 19
    • 0036310254 scopus 로고    scopus 로고
    • From analysis of the crude reaction mixture, we also observe other byproducts which appear to be oligomers containing both cis and trans double bonds. See also: H. Meier, Synthesis 2002, 9, 1213-1228.
    • From analysis of the crude reaction mixture, we also observe other byproducts which appear to be oligomers containing both cis and trans double bonds. See also: H. Meier, Synthesis 2002, 9, 1213-1228.
  • 22
    • 33947481315 scopus 로고    scopus 로고
    • The two enantiomers of trans-cyclooctene have been resolved using chiral silver salts: A. C. Cope, C. R. Ganellin, H. W. Johnson, T. V. Van Auken, H. J. S. Winkler, J. Am. Chem. Soc. 1963, 85, 3276-3279.
    • The two enantiomers of trans-cyclooctene have been resolved using chiral silver salts: A. C. Cope, C. R. Ganellin, H. W. Johnson, T. V. Van Auken, H. J. S. Winkler, J. Am. Chem. Soc. 1963, 85, 3276-3279.
  • 25
    • 0001567777 scopus 로고    scopus 로고
    • IR stretching vibrations matching those seen in reference [9] were seen again by Griffin et al. (see: C. E. Griffin, J. A. Peters, J. Org. Chem. 1963, 28, 1715-1716) using the bis-Wittig reaction described herein.
    • IR stretching vibrations matching those seen in reference [9] were seen again by Griffin et al. (see: C. E. Griffin, J. A. Peters, J. Org. Chem. 1963, 28, 1715-1716) using the bis-Wittig reaction described herein.
  • 27
    • 53549121069 scopus 로고    scopus 로고
    • The Supporting Information contains the crystallographic information file (.cif). CCDC-676888 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • The Supporting Information contains the crystallographic information file (.cif). CCDC-676888 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
  • 31
    • 0027752945 scopus 로고    scopus 로고
    • 13C satellites, but the coupling constants were similar (16 Hz versus 14.8 Hz). However, an NOE signal between the most upfield olefin signal and an ortho proton of the phenyl ring confirmed that it corresponds to the cis olefinic proton. This is in agreement with the assignment made by analogy to the cis olefin in the planar tribenzocyclooctatetraene (at δ = 5.91 ppm), see: X. Wang, X. Hou, Z. Zhou, T. C. W. Mak, H. N. C. Wong, J. Org. Chem. 1993, 58, 7498-7506.
    • 13C satellites, but the coupling constants were similar (16 Hz versus 14.8 Hz). However, an NOE signal between the most upfield olefin signal and an ortho proton of the phenyl ring confirmed that it corresponds to the cis olefinic proton. This is in agreement with the assignment made by analogy to the cis olefin in the planar tribenzocyclooctatetraene (at δ = 5.91 ppm), see: X. Wang, X. Hou, Z. Zhou, T. C. W. Mak, H. N. C. Wong, J. Org. Chem. 1993, 58, 7498-7506.
  • 35
    • 53549087703 scopus 로고    scopus 로고
    • The Supporting Information contains the optimized structure for 3 and the cis,cis isomer, each generated using DFT. The calculations were performed using Jaguar (v. 6.0 and 6.5) with the B3LYP functional, Schrödinger, L. L. C., Portland, OR, 1991-2005. The geometries were optimized using the 6-31G** basis sets, and the energy difference between the two isomers was calculated using the 6-311G** basis sets.
    • The Supporting Information contains the optimized structure for 3 and the cis,cis isomer, each generated using DFT. The calculations were performed using Jaguar (v. 6.0 and 6.5) with the B3LYP functional, Schrödinger, L. L. C., Portland, OR, 1991-2005. The geometries were optimized using the 6-31G** basis sets, and the energy difference between the two isomers was calculated using the 6-311G** basis sets.


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