Rapid Route-Finding for Bifurcating Organic Reactions.


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Article
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Authors
Lee, Sanha 
Goodman, Jonathan M  ORCID logo  https://orcid.org/0000-0002-8693-9136
Abstract

A large number of organic reactions feature post-transition-state bifurcations. Selectivities in such reactions are difficult to analyze because they cannot be determined by comparing the energies of competing transition states. Molecular dynamics approaches can provide answers but are computationally very expensive. We present an algorithm that predicts the major products in bifurcating organic reactions with negligible computational cost. The method requires two transition states, two product geometries, and no additional information. The algorithm correctly predicts the major product for about 90% of the organic reactions investigated. For the remaining 10% of the reactions, the algorithm returns a warning indication that the conclusion may be uncertain. The method also reproduces the experimental and the molecular dynamics product ratios within 15% for more than 80% of the reactions. We have successfully applied the method to a trifurcating organic reaction, a carbocation rearrangement, and solvent-dependent Pummerer-like reactions, demonstrating the power of the algorithm to simplify and to help understand highly complex reactions.

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Keywords
3405 Organic Chemistry, 34 Chemical Sciences, 3407 Theoretical and Computational Chemistry
Journal Title
J Am Chem Soc
Conference Name
Journal ISSN
0002-7863
1520-5126
Volume Title
142
Publisher
American Chemical Society (ACS)
Rights
All rights reserved
Sponsorship
Engineering and Physical Sciences Research Council (EP/P020259/1)
Trinity College, University of Cambridge Cambridge Service for Data Driven Discovery (CSD3) operated by the University of Cambridge Research Computing Service (www.csd3.cam.ac.uk), provided by Dell EMC and Intel using Tier-2 funding from the Engineering and Physical Sciences Research Council (capital grant EP/P020259/1)
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