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Effect of a chiral electrostatic cavity on product selection in a reaction with a bifurcating reaction path

Carpenter, Barry K. 2014. Effect of a chiral electrostatic cavity on product selection in a reaction with a bifurcating reaction path. Theoretical Chemistry Accounts 133 (8) , 1525. 10.1007/s00214-014-1525-2

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Abstract

The possibility of influencing the selection of product-forming branches in a reaction with a bifurcating reaction path is explored. The reaction chosen is a substituted version of the well-known ring opening of singlet cyclopropanylidene. The substituents are arranged such that the starting carbene is meso (i.e., achiral) but the products are enantiomeric allenes. The question being posed is whether optical activity can be induced in the products by choosing the reaction to occur within a chirally disposed set of point charges. Direct-dynamics trajectory calculations are used to address the problem. It is found that, on a microscopic level, the point charges have a very significant effect on the choice of bifurcation branch. However, when the individual microscopic effects are averaged, to take account of free rotation of the molecule with respect to the charge array, the net effect is small (about 3 % enantiomeric excess after 500 fs). Nevertheless, even this small effect is larger than one might have predicted on the basis of an earlier analysis of electrostatic contributions to the interactions between chiral molecules. The reason is that the present simulation involves a concentric arrangement of chiral, polar objects, whereas the earlier analysis considered only a side-by-side arrangement. Through the use of numerical simulation, it is shown that two freely rotating arrays of chiral point charges exhibit larger diastereomeric discrimination when the arrays are concentric than when they are not, even for comparable average distances between the charges.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Advanced Research Computing @ Cardiff (ARCCA)
Chemistry
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: Direct dynamics; optical activity induction; reaction path bifurcation.
Publisher: Springer
ISSN: 1432-881X
Funders: EPSRC, NSF
Last Modified: 18 Feb 2019 12:14
URI: http://orca-mwe.cf.ac.uk/id/eprint/61415

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