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22
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64549131673
-
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-1)so that the corresponding pathway is not expected to take place.
-
-1)so that the corresponding pathway is not expected to take place.
-
-
-
-
24
-
-
64549147057
-
-
-1/6, according to: Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry; Pergamon Press: Oxford, 1999; p 303.
-
-1/6, according to: Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry; Pergamon Press: Oxford, 1999; p 303.
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-
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25
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64549118189
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-
This attribution agrees with the trend of the 1H shift of the corresponding methyl groups, that of 1a (2.02 ppm) being at lower field with respect to that of 1b 1.68 ppm, The latter should thus correspond to the anti structure since its methyl groups lie in a position where they experience the upfield shift displacement due to the aromatic ring currents; see: Jackman, L. M, Sternhell, S. Applications of NMR Spectroscopy in Organic Chemistry, 2nd ed, Pergamon Press: Oxford, 1969; p 95. Jennings, W. B, Farrell, B. M, Malone, J. F Acc. Chem. Res. 2001, 34, 885-894
-
1H shift of the corresponding methyl groups, that of 1a (2.02 ppm) being at lower field with respect to that of 1b (1.68 ppm). The latter should thus correspond to the anti structure since its methyl groups lie in a position where they experience the upfield shift displacement due to the aromatic ring currents; see: Jackman, L. M.; Sternhell, S. Applications of NMR Spectroscopy in Organic Chemistry, 2nd ed.; Pergamon Press: Oxford, 1969; p 95. Jennings, W. B.; Farrell, B. M.; Malone, J. F Acc. Chem. Res. 2001, 34, 885-894.
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-
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-
26
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17044446282
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9 predict an upfield methyl shift for the anti (1.71 ppm) with respect to the syn 2.16 ppm, in agreement with the observed trend
-
9 predict an upfield methyl shift for the anti (1.71 ppm) with respect to the syn (2.16 ppm), in agreement with the observed trend.
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(2003)
Angew. Chem. Int. Ed
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Wuthrich, K.1
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27
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64549130394
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For the assignments made by TDDFT-CD calculations, see: Diedrich, C; Grimme, S. J.Phys. Chem. A 2003, 107, 2524. Stephens, P. J.; McCann, D. M.; Butkus, E.; Stoncius, S.; Cheeseman, J. R.; Frisch, M. J J. Org. Chem. 2004, 69, 1948.
-
For the assignments made by TDDFT-CD calculations, see: Diedrich, C; Grimme, S. J.Phys. Chem. A 2003, 107, 2524. Stephens, P. J.; McCann, D. M.; Butkus, E.; Stoncius, S.; Cheeseman, J. R.; Frisch, M. J J. Org. Chem. 2004, 69, 1948.
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28
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2942665493
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Stephens, P. J.; McCann, D. M.; Devlin, F. J.; Cheeseman, J. R.; Frisch, M. J J. Am. Chem. Soc. 2004, 126, 7514.
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22944437428
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33747422844
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34047224863
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36
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34047198339
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It has to be pointed out that the experimental interconversion is accomplished via the rotation of either of the two naphthalene rings, whereas the computed value was obtained assuming the rotation of only one ring. Thus, for an appropriate comparison the experimental rate constant should be divided by 2 see, for instance: Lunazzi, L, Mazzanti, A, Minzoni, M. J. Org. Chem. 2007, 72, 2501-2507
-
It has to be pointed out that the experimental interconversion is accomplished via the rotation of either of the two naphthalene rings, whereas the computed value was obtained assuming the rotation of only one ring. Thus, for an appropriate comparison the experimental rate constant should be divided by 2 (see, for instance: Lunazzi, L.; Mazzanti, A.; Minzoni, M. J. Org. Chem. 2007, 72, 2501-2507.
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37
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Lunazzi, L.; Mazzanti, A.; Ran, S.; Rao, S.P. J. Org. Chem. 2008, 73, 678-688).
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38
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64549132918
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Accordingly, the value of the experimental barrier which actually corresponds to the rotation of a single ring becomes slightly higher, i.e, 35.9 kcal mol-1
-
-1.
-
-
-
-
39
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64549110236
-
-
The presence of two substituents might be responsible for the observed interconversion barrier as a consequence of a possible buttressing effect
-
The presence of two substituents might be responsible for the observed interconversion barrier as a consequence of a possible buttressing effect.
-
-
-
-
40
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33847088636
-
-
2 solution when using a 37:1 molar excess of enantiopure (R)-(-)-2, 2, 2-trifluoro-1-(9-anthryl)ethanol; see: Pirkle, W. H.; Sikkenga, D. L.; Pavlin, M. S. J. Org. Chem. 1977, 42, 384-387.
-
2 solution when using a 37:1 molar excess of enantiopure (R)-(-)-2, 2, 2-trifluoro-1-(9-anthryl)ethanol; see: Pirkle, W. H.; Sikkenga, D. L.; Pavlin, M. S. J. Org. Chem. 1977, 42, 384-387.
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41
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33845470896
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Prepared according to: Thompson, W. J.; Gaudino, J. J. Org. Chem. 1984, 49, 5237.
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Prepared according to: Thompson, W. J.; Gaudino, J. J. Org. Chem. 1984, 49, 5237.
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42
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41849093315
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