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Rompietti, R.5
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68
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Dissimilarities between the conformations in solution with respect to the structures found in the solids have been reported; see: Johansen, J. T, Vallee, B. L. Proc. Nat. Acad. Sci. U.S.A. 1971, 68, 2532-2535
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Dissimilarities between the conformations in solution with respect to the structures found in the solids have been reported; see: Johansen, J. T.; Vallee, B. L. Proc. Nat. Acad. Sci. U.S.A. 1971, 68, 2532-2535.
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70
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0030794823
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Burke, L. P.; DeBellis, A. D.; Fuhrer, H.; Meier, H.; Pastor, S. D.; Rihs, G.; Rist, G.; Rodebaugh, R. K.; P. Shum, S. P. J. Am. Chem. Soc. 1997, 119, 8313-8323.
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Coluccini, C.1
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84989078630
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Perry, N. B.; Blunt, J. W.; Munro, M. H. Magn. Reson. Chem. 2005, 27, 624-627.
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Perry, N.B.1
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Munro, M.H.3
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74
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17444369440
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A situation where it has been unambiguously demonstrated that the structure observed by X-ray diffraction in the crystal is that of the minor conformer present in solution has been reported in: Lunazzi, L, Mazzanti, A, Minzoni, M, Anderson, J. E. Org. Lett. 2005, 7, 1291-1294
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A situation where it has been unambiguously demonstrated that the structure observed by X-ray diffraction in the crystal is that of the minor conformer present in solution has been reported in: Lunazzi, L.; Mazzanti, A.; Minzoni, M.; Anderson, J. E. Org. Lett. 2005, 7, 1291-1294.
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75
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41849090046
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It has to be taken into account that the syn conformer exists as four degenerate forms (two identical pairs of enantiomers, whereas the anti-in exists solely as two degenerate forms, corresponding to a pair of enantiomers (the presence of the anti-out can be, in practice, neglected, since its higher relative energy of 0.9 kcal mol-1 would correspond to a proportion lower than 8% at -92°C, Owing to the greater probability, the actual population of the syn conformer might be higher than expected solely on the basis of its computed energy. In fact, both of the anti forms belong to the C2 point group and are therefore disfavored by RT In 2 i.e, 0.24 kcal mol-1 at -92° C, see: Eliel, E. L, Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 97 and 601, Accordingly, when corrected for this factor the energy difference becomes 0.06 kcal mol-1, a value that corresponds to an anti/syn ratio o
-
-1, a value that corresponds to an anti/syn ratio of 54/46. When the proportions are so close to 50/50, the approximations involved in the computed energy do not allow one to obtain a reliable assignment for the situation in solution because, in these conditions, even a small solvent effect might cause a reversal of the assignment.
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77
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41849106417
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Combrisson, S.; Roques, B.; Rigny, P.; Basselier, J. J. Can J. Chem. 1971, 49, 904-918.
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79
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84987321344
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When the rotation about the aryl-biphenylene bond is frozen, the methylene hydrogens are diastereotopic because the conformers adopt a non planar conformation. For the same reason are diastereotopic at low temperature the methyl groups of the isopropyl moieties of compound 3. See: Mislow, K.; Raban, M. Top. Stereochem. 1967, 1, 1.
-
When the rotation about the aryl-biphenylene bond is frozen, the methylene hydrogens are diastereotopic because the conformers adopt a non planar conformation. For the same reason are diastereotopic at low temperature the methyl groups of the isopropyl moieties of compound 3. See: Mislow, K.; Raban, M. Top. Stereochem. 1967, 1, 1.
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82
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Casarini, D.; Lunazzi, L.; Macciantelli, D. J. Chem. Soc, Perkin Trans 1992, 2, 1363.
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0004028219
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Newman, M. S, Ed, John Wiley and Sons, Inc, New York, Chapter 12
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(a) Westheimer, F. H. In Steric Effects in Organic Chemistry; Newman, M. S., Ed.; John Wiley and Sons, Inc.: New York, 1956; Chapter 12.
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(b) Karnes, H. A.; Rose, M. L.; Collat, J. W.; Newman, M. S. J. Am. Chem. Soc. 1968, 90, 458-461.
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87
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10044258627
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32044446749
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Schlosser, M.1
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90
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41849102691
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-
Irradiation (Figure S-2 of the Supporting Information) of the major signal of the methyls in position 3,3′ of the xylyl rings (1.67 ppm) of 5, yields enhancement for the major signal of the corresponding hydrogens in position 4,4′ (6.90 ppm) of the same xylyl rings and for the major signal of the hydrogens in positions 5′,5 (6.96 ppm) of the other ring, as expected for an anti conformer, where the latter distance is short enough to produce NOE effects. On the contrary irradiation of the minor signal (1.86 ppm) of the methyls in position 3,3′ of the xylyl rings, enhances solely the minor signal of the corresponding hydrogens in position 4,4′ of the same ring (6.74 ppm, Likewise irradiation of the major signals of the methyl in positions 2,2′ of the xylyl rings (1.37 ppm) enhances the corresponding signals of the hydrogens in positions 2,7 of the biphenylene moiety (6.59 ppm) and also that of the hydrogens in positions 6′,6 of the other x
-
Irradiation (Figure S-2 of the Supporting Information) of the major signal of the methyls in position 3,3′ of the xylyl rings (1.67 ppm) of 5, yields enhancement for the major signal of the corresponding hydrogens in position 4,4′ (6.90 ppm) of the same xylyl rings and for the major signal of the hydrogens in positions 5′,5 (6.96 ppm) of the other ring, as expected for an anti conformer, where the latter distance is short enough to produce NOE effects. On the contrary irradiation of the minor signal (1.86 ppm) of the methyls in position 3,3′ of the xylyl rings, enhances solely the minor signal of the corresponding hydrogens in position 4,4′ of the same ring (6.74 ppm). Likewise irradiation of the major signals of the methyl in positions 2,2′ of the xylyl rings (1.37 ppm) enhances the corresponding signals of the hydrogens in positions 2,7 of the biphenylene moiety (6.59 ppm) and also that of the hydrogens in positions 6′,6 of the other xylyl ring (6.96 ppm). On the contrary, irradiation of the minor signal of the methyl groups (1.76 ppm) enhances solely the corresponding H2,7 minor signal of biphenylene (6.60 ppm), as expected for a syn conformer where the distance between the hydrogens of the methyl in position 2 of one ring and the hydrogen in position 6′ of the other ring is too large to yield a NOE effect.
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91
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41849109437
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The conformational assignment in compounds 3 and 4 was obtained by means of the mentioned low temperature NOE experiments.
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The conformational assignment in compounds 3 and 4 was obtained by means of the mentioned low temperature NOE experiments.
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92
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41849147101
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2) employed for measuring the barriers of compounds 1-3 and 5.
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2) employed for measuring the barriers of compounds 1-3 and 5.
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93
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41849084443
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The lower proportion of the conformer anti observed in compound 4 with respect to 3 might be also interpreted as the consequence of a statistic effect, due to the possibility of having both the anti-in and anti-out situations in the case of 3, whereas solely a single anti form occurs in 4.
-
The lower proportion of the conformer anti observed in compound 4 with respect to 3 might be also interpreted as the consequence of a statistic effect, due to the possibility of having both the anti-in and anti-out situations in the case of 3, whereas solely a single anti form occurs in 4.
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94
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4644357388
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Lunazzi, L.; Mazzanti, A. J. Am. Chem. Soc. 2004, 126, 12155-12157. See also ref 10c.
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Lunazzi, L.; Mazzanti, A. J. Am. Chem. Soc. 2004, 126, 12155-12157. See also ref 10c.
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95
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41849085143
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6 lies in a position that does not interfere with the signals of 6b).
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6 lies in a position that does not interfere with the signals of 6b).
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96
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41849130591
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The isomer anti (6b) displays a methyl signal at a substantially higher field than the methyl signal of the isomer syn (6a) owing to the effect of the aromatic ring currents, since in the anti situation the methyl groups lie above the plane of the naphthalene rings, see: Jackman, L. M.; Sternhell, S. Applications of NMR Spectroscopy in Organic Chemistry, 2nd ed.; Pergamon Press: Oxford, 1969; p 95.
-
The isomer anti (6b) displays a methyl signal at a substantially higher field than the methyl signal of the isomer syn (6a) owing to the effect of the aromatic ring currents, since in the anti situation the methyl groups lie above the plane of the naphthalene rings, see: Jackman, L. M.; Sternhell, S. Applications of NMR Spectroscopy in Organic Chemistry, 2nd ed.; Pergamon Press: Oxford, 1969; p 95.
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0037040637
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Dell' Erba, C.; Gasparrini, F.; Grilli, S.; Lunazzi, L.; Mazzanti, A.; Novi, M.; Pierini, M.; Tafani, C.; Villani, C. J. Org. Chem. 2002, 67, 1663-1668.
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101
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0037431283
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