Reaction Networks, A Simplification Attempt

2016-10-04T19:54:00Z (GMT) by Dmitrij Rappoport
Complex chemical reactions present significant challenges for automatic explorated by computational tools due to the involved topology of the corresponding reactive potential energy surface (PES) with many energy minima connected by transition states. In our previous work, we have developed the Heuristically-Aided Quantum Chemistry (HAQC) approach to modeling complex chemical reactions, which leverages the existing empirical rules of polar organic reactions as powerful heuristics for selecting plausible reactive transformations, followed by structure optimizations using quantum chemical methods. The HAQC approach makes use of heuristic kinetic criteria for selecting reaction paths that are not only plausible, that is, consistent with the empirical rules of organic reactivity, but are feasible under the reaction conditions. In this work, we develop heuristic kinetic feasilibity crieria with broad applicability to polar (substitutions, additions, and eliminations) and pericyclic organic reactions (cyclizations, sigmatropic shifts, and cycloadditions). Moreover, we are able to show that a consistent set of heuristic parameters is suitable for classifying reaction paths as feasible or unfeasible for the reactions considered.