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The use of steric energy resulting from Newtonian mechanics-based molecular modelling techniques is sometimes warranted by the fact that, unlike regioselectivity which can depend on electronic factors, enantioselectivity is almost completely steric. There are however many recent reports which relate on the observation of large electronic effects on the enantioselectivity of catalytic reactions: Schnyder A., Hintermann L., Togni A., Angew. Chem. Int. Ed. Engl., 1995, 34, 931, and references cited therein. In order to keep from the former assumptions, we preferred to base our analyses on total energy which include electronic factors.
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A combination of molecular mechanics and ab initio methods applicable to the prediction of stereochemistries of Lewis-acid catalyzed reactions of chiral acrylates with dienes has recently been reported: de Pascual-Teresa B., Gonzalez J., Alonsio A., Houk K. N., J. Am. Chem. Soc., 1995, 117, 4347.
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Numerous alternative conformations of the seven-membered metallacycle have been evaluated. In particular, minimizations conducted on a twist-boat conformation with the nitrogen atom in the P(N)-Rh-P(O) plane often led to the distorted chair conformation 2. Therefore, the latter conformation was systematically investigated.
-
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63
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0024961560
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The nucleophilic attack of the H atom to the carbonyl C atom yielding an alkoxy rhodium species is commonly accepted for the hydride migration step (see reference 11). The formation of an hydroxyalkyl rhodium species has been suggested to occur in the presence of amines as promotors; see: Chan A. S. C., Landis C. R., J. Mol. Catal., 1989, 49, 165.
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27844473275
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note
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2.
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