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Can the π-FaciaI Selectivity of Solvation Be Predicted by Atomistic Simulation?
- Source :
-
Journal of the American Chemical Society . 8/3/2005, Vol. 127 Issue 30, p10699-10706. 8p. - Publication Year :
- 2005
-
Abstract
- This work is concerned with the rationalization and prediction of solvent and temperature effects in nucleophilic addition to α-chiral carbonyl compounds leading to facial diastereoselectivity. We study, using molecular dynamics simulations, the facial solvation of (R)-2-phenyl-propionaldehyde in n-pentane and n-octane at a number of temperatures and compare it with experimental selectivity data for the nBuLi addition leading to syn- and anti-(2R)-2-phenyl-3-heptanol, which give nonlinear Eyring plots with the presence of inversion temperatures. We have found from simulations that the facial solvation changes with temperature and alkane. Moreover, by introducing a suitable molecular chirality index we have been able to predict break temperatures (Tcl) for the two solvents within less than 20° of the inversion temperatures experimentally observed in the diastereoselective nBuLi addition. We believe this could lead to a viable approach for predicting inversion temperatures and other subtle solvent effects in a number of stereoselective reactions. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00027863
- Volume :
- 127
- Issue :
- 30
- Database :
- Academic Search Index
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 17814083
- Full Text :
- https://doi.org/10.1021/ja052199r