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Volumn 131, Issue 14, 2009, Pages 5233-5243

Ring strain energy in the cyclooctyl system. the effect of strain energy on [3 + 2] cycloaddition reactions with azides

Author keywords

[No Author keywords available]

Indexed keywords

4-OCTYNE; ACETAMIDO; ACTIVATION BARRIERS; ALLENES; CYCLOADDITION REACTION; CYCLOALKENES; CYCLOHEPTENE; CYCLOHEXENE; CYCLOOCTANE; CYCLOOCTENE; EFFECT OF STRAIN ENERGY; METHYL AZIDE;

EID: 67849087099     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8094137     Document Type: Article
Times cited : (95)

References (63)
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    • See also, May 5, p
    • (e) See also Chem. Eng. News 2008, May 5, p 8.
    • (2008) Chem. Eng. News , pp. 8
  • 20
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    • For recent discussions of the methods for the calculation of ring SEs, see: a
    • For recent discussions of the methods for the calculation of ring SEs, see: (a) Khoury, P. R.; Goddard, J. D.; Tam, W. Tetrahedron 2004, 60, 8103.
    • (2004) Tetrahedron , vol.60 , pp. 8103
    • Khoury, P.R.1    Goddard, J.D.2    Tam, W.3
  • 27
    • 67849104788 scopus 로고    scopus 로고
    • The G3 protocol in Gaussian 03 utilizes an optimized geometry refined at the MP2(full)/ 6-31G(d) level. The total energy is then refined using a series of single point calculations at higher levels of theory than includes, in general, a correction for diffuse functions [MP4/6-31+G(d)]; a correction for higher polarization functions on non-hydrogen atoms and polarization p-functions on hydrogen [MP4/6-31+G(2df,p)]; a correction for correlation effects beyond fourth-order perturbation theory [QCISD(T, E4T)/6-31G(d)]; a correction for larger basis set effects [MP2(full)/ G3large].
    • (b) The G3 protocol in Gaussian 03 utilizes an optimized geometry refined at the MP2(full)/ 6-31G(d) level. The total energy is then refined using a series of single point calculations at higher levels of theory than includes, in general, a correction for diffuse functions [MP4/6-31+G(d)]; a correction for higher polarization functions on non-hydrogen atoms and polarization p-functions on hydrogen [MP4/6-31+G(2df,p)]; a correction for correlation effects beyond fourth-order perturbation theory [QCISD(T, E4T)/6-31G(d)]; a correction for larger basis set effects [MP2(full)/ G3large].
  • 32
    • 56449122060 scopus 로고    scopus 로고
    • For an excellent critique of this controversy see
    • (d) For an excellent critique of this controversy see: Poutsma, M. L. J. Org. Chem. 2008, 73, 8921.
    • (2008) J. Org. Chem , vol.73 , pp. 8921
    • Poutsma, M.L.1
  • 33
    • 84869583977 scopus 로고    scopus 로고
    • For the cyclization method the equation SE ) Ecyclic- Eacyclic- ECorr was used to estimate the SE. The energy balancing terms required are the breaking two C-H bonds and forming one C-C bond. All energies reported are total energies from G3 calculations; ECorr ) 2EC-H- EC-C + 2EH 2(ECH3CH2CH2CH3- ECH3CH2CH2CH2·)-(En-octane- 2ECH3CH2CH2CH2·) + 2(EH) )-1.180743 where EH ) (-0.501003 au) at the G3 level and EC-H ) the energy difference between n-butane and its terminal primary free radical and H atom (-0.158949 au); EC-C ) the energy difference between n-octane and two primary n-butane free radicals (-0.139161 au) with an Ecorr)-1.180743 au.
    • (a) For the cyclization method the equation SE ) Ecyclic- Eacyclic- ECorr was used to estimate the SE. The energy balancing terms required are the breaking two C-H bonds and forming one C-C bond. All energies reported are total energies from G3 calculations; ECorr ) 2EC-H- EC-C + 2EH ) 2(ECH3CH2CH2CH3- ECH3CH2CH2CH2·)-(En-octane- 2ECH3CH2CH2CH2·) + 2(EH) )-1.180743 where EH ) (-0.501003 au) at the G3 level and EC-H ) the energy difference between n-butane and its terminal primary free radical and H atom (-0.158949 au); EC-C ) the energy difference between n-octane and two primary n-butane free radicals (-0.139161 au) with an Ecorr)-1.180743 au.
  • 34
    • 67849086989 scopus 로고    scopus 로고
    • For Z-4-octene EC-H )-0.159006 au, the energy difference between Z-4-octene and its primary terminal free radical + H atom and EC-C )-0.139161 au with an Ecorr -1.180857 au.
    • (b) For Z-4-octene EC-H )-0.159006 au, the energy difference between Z-4-octene and its primary terminal free radical + H atom and EC-C )-0.139161 au with an Ecorr )-1.180857 au.
  • 35
    • 67849121626 scopus 로고    scopus 로고
    • For E-4- octene EC-H )-0.159316 au, the energy difference between E-4- octene and its primary terminal free radical + H atom and EC-C )- 0.139161 au with an Ecorr -1.181477 au.
    • (c) For E-4- octene EC-H )-0.159316 au, the energy difference between E-4- octene and its primary terminal free radical + H atom and EC-C )- 0.139161 au with an Ecorr )-1.181477 au.
  • 36
    • 67849097490 scopus 로고    scopus 로고
    • For 4-octyne EC-H )- 0.159484 au, the energy difference between 4-octyne and its primary terminal free radical + H atom and EC-C )-0.139161 au with an Ecorr -1.181813 au.
    • (d) For 4-octyne EC-H )- 0.159484 au, the energy difference between 4-octyne and its primary terminal free radical + H atom and EC-C )-0.139161 au with an Ecorr )-1.181813 au.
  • 37
    • 67849103901 scopus 로고    scopus 로고
    • For 3,3-difluoro-4-octyne EC-H )-0.16054 au, the energy difference between 3,3-difluoro-4-octyne and its primary terminal free radical + H atom and EC-C )-0.139161 au with an Ecorr -1.183925 au.
    • (e) For 3,3-difluoro-4-octyne EC-H )-0.16054 au, the energy difference between 3,3-difluoro-4-octyne and its primary terminal free radical + H atom and EC-C )-0.139161 au with an Ecorr )-1.183925 au.
  • 38
    • 0001043503 scopus 로고    scopus 로고
    • For a thorough discussion of the various conformations of cyclooctane and cyclononane calculated at the MP2 level see: (a) Rocha, W. R, Pliego, J. R, Jr, Resende, S. M, Dos Santos, H. F, De Oliveira, M. A, De Almeida, W. B. J. Comput. Chem. 1998, 19, 524
    • For a thorough discussion of the various conformations of cyclooctane and cyclononane calculated at the MP2 level see: (a) Rocha, W. R.; Pliego, J. R., Jr.; Resende, S. M.; Dos Santos, H. F.; De Oliveira, M. A.; De Almeida, W. B. J. Comput. Chem. 1998, 19, 524.
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    • This controversy preceded the introduction of diastereotopic hydrogens (Mislow and Raban In Topics in Stereochemistry; 1967; 1, p 2, and it was difficult at that time to comprehend how the NMR of two enantiomers could differ. E-Cyclooctene exhibits a multiplet in its proton NMR spectrum centered upfield at ≈0.5 ppm as a consequence of two hydrogens of the C5-C6 fragment buried in the π-cloud of the transannular CdC. Interconversion of the twist with the chair conformer of, )-E-cyclooctene, by twisting the C5-C6 fragment through the ring, exchanges the environment of these two hydrogens in and out of the π-cloud while maintaining the same absolute configuration of the CdC. A sterospecific synthesis of E-cyclooctene, with stereospecific deuteration at C5-C6, could have provided a conformational assignment of this diastereomeric alkene. Unfortunately, the untimely death of Professor Cope on June 4, 1966, prevented compl
    • This controversy preceded the introduction of diastereotopic hydrogens (Mislow and Raban In Topics in Stereochemistry; 1967; Vol. 1, p 2), and it was difficult at that time to comprehend how the NMR of two "enantiomers" could differ. E-Cyclooctene exhibits a multiplet in its proton NMR spectrum centered upfield at ≈0.5 ppm as a consequence of two hydrogens of the C5-C6 fragment buried in the π-cloud of the transannular CdC. Interconversion of the twist with the chair conformer of (+)-E-cyclooctene, by twisting the C5-C6 fragment through the ring, exchanges the environment of these two hydrogens in and out of the π-cloud while maintaining the same absolute configuration of the CdC. A sterospecific synthesis of E-cyclooctene, with stereospecific deuteration at C5-C6, could have provided a conformational assignment of this diastereomeric alkene. Unfortunately, the untimely death of Professor Cope on June 4, 1966, prevented completion of these experiments.
  • 47
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    • For a study on the mechanism of the thermal isomerization of E-cyclooctene see: Andrews, U. H.; Baldwin, J. E.; Grayston, M. W. J. Org. Chem. 1982, 47, 287.
    • (b) For a study on the mechanism of the thermal isomerization of E-cyclooctene see: Andrews, U. H.; Baldwin, J. E.; Grayston, M. W. J. Org. Chem. 1982, 47, 287.
  • 48
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    • For earlier ab initio studies on E-cycloheptene see: (a) Cain, D.; Pawar, D. M.; Noe, E. A. J. Mol. Struct. (Theochem) 2004, 674, 251.
    • For earlier ab initio studies on E-cycloheptene see: (a) Cain, D.; Pawar, D. M.; Noe, E. A. J. Mol. Struct. (Theochem) 2004, 674, 251.
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    • Bach, R. D. In The Chemistry of Peroxides; Rappoport, Z., Ed.; Wiley: New York, 2006; Vol. 2, Part 1, pp 1-92.
    • (2006) The Chemistry of Peroxides , vol.2 , Issue.PART 1 , pp. 1-92
    • Bach, R.D.1
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    • Gaussian, Inc, Pittsburgh, PA, See the Supporting Information for the full list of authors
    • (b) Gaussian 03, revision B.05 (SGI64-G03RevB.05); Gaussian, Inc.: Pittsburgh, PA, 2003. See the Supporting Information for the full list of authors.
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