Identification and analysis of synthesis routes in complex catalytic reaction networks for biomass upgrading

In this paper, we present a method to construct and query the spectrum (>15,000) of potential biomass-derived compounds that can be synthesized using heterogeneous catalysis. Specifically, it involves the construction of an exhaustive network of reactions using RING, a rule-based network generator that we have developed, to identify potentially synthesizable compounds from biomass. Subsequently, we: (a) employ quantitative structure-property relationships to query compounds with desired properties, (b) seek different synthesis routes to these compounds, and (c) evaluate these routes in terms of stoichiometric, energetics, and physical parameters such as atom efficiency, enthalpy and free energy change of reactions, and aqueous-organic partition coefficients (Log. P) of intermediates. Thermochemistry and Log. P are both estimated using group additivity methods, and all property estimations are performed on-the-fly during network generation. We present this method in context of identifying and evaluating heterogeneous catalytic routes from biomass to fatty alcohols that are potential constituents of nonionic surfactants. We also show that group additivity-based estimates of enthalpy of reaction are accurate to within 10. kJ/mol and Log. P values reliably predict the relative hydrophobicity of compounds. This method is generic, flexible, reliable and fast in terms of the scope of chemistry that can be considered, properties that can be included, predictive accuracy, and speed of execution; it can, therefore, be used to rapidly screen a large spectrum of compounds and synthesis routes in biomass conversion.