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0035905532
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(b) Li, J.; Burgett, A. W. G.; Esser, L.; Amezeva, C.; Harran, P. G. Angew. Chem., Int. Ed. 2001, 40, 4770-4773.
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84986437005
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1 = H) using the directed Monte Carlo algorithm of Macromodel 6.5 (cf.: Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440-467) led to a family of four low-energy conformers corresponding to the four possible atropisomers about the indicated biaryl linkages. Two of these species were of equivalently low energy, 3 as shown and its rotomer about the C(24)/C(26) bond. However, only 3 among these conformers brings C(10) and C(30) within bonding distance, 3.51 Å. The enthalpies of rotation about the C(24)/C(25) and C(16)/C(18) bonds were estimated by the difference between the "global minimum" conformer 3 and planar versions of 3 where the relevant biaryl dihedral was locked at either 0° or 180°, The four values obtained (two rotational directions per bond) are shown with 3. Only rotation about the C(24)/C(26) bond in one direction is predicted by this analysis to be facile at room temperature (Δ/H‡ ≈ 14 kcal/mol).
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0026572606
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29
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0043273331
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note
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int of 0.09 (after absorption correction), limits the crystallographic R-factor to 0.18 for this structure. Nevertheless, the relative stereochemical assignment of interest here is unambiguous.
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