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(e) See also Chem. Eng. News 2008, May 5, p 8.
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For recent discussions of the methods for the calculation of ring SEs, see: a
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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.
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0001311982
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and references therein
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(b) Schleyer, P. von R.; Willams, J. E.; Blanchard, K. R. J. Am. Chem. Soc. 1970, 92, 2337.
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27
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67849104788
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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].
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29
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33748588933
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(a) Schreiner, P. R.; Fokin, A. A.; Pascal, R. A.; Meijere, A. de. Org. Lett. 2006, 3635.
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Org. Lett
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Schreiner, P.R.1
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Meijere4
de, A.5
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30
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34748902875
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(b) Wodrich, M. D.; Wannere, C. S.; Mo, Y.; Jarowski, P. D.; Houk, K. N.; Schleyer, P. von R. Chem. Eur. J. 2007, 13, 7731.
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(c) Zavitsas, A. A.; Matsunaga, N.; Rogers, D. W. J. Phys. Chem. A 2008, 112, 5734.
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Zavitsas, A.A.1
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32
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56449122060
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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.
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J. Org. Chem
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Poutsma, M.L.1
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33
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84869583977
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-
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
-
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67849086989
-
-
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
-
-
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
-
-
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
-
-
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
-
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0001043503
-
-
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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39
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33846315107
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(b) Franco, M. L.; Ferreira, D. E. C.; Dos Santos, H. F.; De Almeida, W. B. Int. J. Quantum Chem. 2007, 107, 545.
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Franco, M.L.1
Ferreira, D.E.C.2
Dos Santos, H.F.3
De Almeida, W.B.4
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41
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84869583974
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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.
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0344087153
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(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.
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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.
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