Concentration-Flux-Steered Mechanism Exploration with an Organocatalysis Application

Abstract

Investigating a reactive chemical system with automated reaction network exploration algorithms provides a more detailed picture of its chemical mechanism than what would be accessible by manual investigation. In general, exploration algorithms cannot uncover reaction networks exhaustively for feasibility reasons. They should therefore decide which part of a network is kinetically relevant under some external conditions given. Here, we propose an automated algorithm that identifies and explores kinetically accessible regions of a reaction network on the fly by explicit modeling of concentration fluxes through an (incomplete) reaction network that is emerging during automated first-principles exploration. Key compounds are automatically identified and selected for the continuation of the exploration. As an example, we explore the reaction network of the multi-component proline-catalyzed Michael addition of propanal and nitropropene. Our algorithm provides a mechanistic picture of the Michael addition in unprecedented detail.

36 pages, 10 figures

References in corpus (4)

• Context-Driven Exploration of Complex Chemical Reaction Networks
• Autonomous Reaction Network Exploration in Homogeneous and Heterogeneous Catalysis
• Expansive Quantum Mechanical Exploration of Chemical Reaction Paths
• On the Predictive Power of Chemical Concepts

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• Predicting long timescale kinetics under variable experimental conditions with Kinetica.jl
• Automated Exploration of Radical-Molecule Chemistry: The Case of Oxirane + CH in the ISM