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12244303328
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note
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2 workstation (Silicon Graphics, Inc., CA). The geometry of sarcophine (3) was initially constructed by reference to its X-ray data reported in ref 11. This geometry was then optimized at the PM3 to obtain the most stable conformation of 3. The geometries of 13-hydroxysarcophines were constructed on the basis of this conformation and then optimized at the PM3.
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15
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12244291574
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note
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The obtained PM3 geometries of 13-hydroxysarcophines show that the distance between H-13 and H-2β is 2.35 A in the S-configuration, while it is 4.04 Å in the R-configuration and that the dihedral angles between H-13 and H-14 are -84.1° and 158.8° in the S-configuration, while they are 50.5° and 165.2° in the R-configuration.
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16
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12244306567
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note
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1H NMR spectrum, the ratio for the formation of 7a/7b is 75:25.
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18
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0004124913
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Wavefunction, Inc.: CA
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All geometries were initially constructed on the basis of the most stable conformation of 3 and then subjected to optimization for the intermediates (8 and 9) or to search for the transition state (TS) at the PM3. All energies were calculated using the PM3 geometries at the pBP/DN* level. Energetic results for numerical basis sets DN* have been reported to be similar to those for Gaussian basis sets 6-31G*. See: Hehre, W. J.; Yu, J.; Kluzinger, P. E.; Lou, L. In A Brief Guide to Molecular Mechanics and Quantum Chemical Calculations; Wavefunction, Inc.: CA, 1998; p 28.
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A Brief Guide to Molecular Mechanics and Quantum Chemical Calculations
, pp. 28
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Hehre, W.J.1
Yu, J.2
Kluzinger, P.E.3
Lou, L.4
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19
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12244311543
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note
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Conformational analysis was carried out using the Osawa method in conjunction with MMFF94 molecular mechanics starting from the most stable conformation of 3.
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20
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12244300594
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note
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The conformers B and C are 6 kcal/mol higher in potential energy than the conformer A, the global minimum conformer. These energies were calculated at the pBP/DN* after the PM3 geometry optimization of conformers, generated by use of the conformational analysis.
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21
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12244271114
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note
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The HOMO energies of the conformer A, B, and C are respectively -0.221, -0.220, and -0.222 hartrees at the pBP/DN* level.
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22
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33746589279
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Czarkie, D.; Groweiss, A.; Kashman, Y. Tetrahedron 1985, 41, 1049-1056.
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Tetrahedron
, vol.41
, pp. 1049-1056
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Czarkie, D.1
Groweiss, A.2
Kashman, Y.3
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23
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85010178330
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Kobayashi, M.; Ishizaka, T.; Miura, N.; Mitsuhashi, H. Chem. Pharm. Bull. 1987, 35, 2314-2318.
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Mitsuhashi, H.4
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25
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0032538584
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El Sayed, K. A.; Hamann, M. T.; Wadding, C. A.; Jensen, C.; Lee, S. K.; Dunstan, C. A.; Pezzuto, J. M. J. Org. Chem. 1998, 63, 7449-7455.
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J. Org. Chem.
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El Sayed, K.A.1
Hamann, M.T.2
Wadding, C.A.3
Jensen, C.4
Lee, S.K.5
Dunstan, C.A.6
Pezzuto, J.M.7
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