Hybrid biological and chemocatalytic processes present a unique opportunity to convert biomass into renewable, high-value platform chemicals. cis,cis-Muconic acid is a C6 polyunsaturated dicarboxylic acid that can be derived biologically from both sugar and lignin for subsequent multistep catalytic conversion to dimethyl terephthalate, a large-market commodity chemical for polymer production, or to novel, functionally alternative cyclic monomers. This upgrading pathway involves (i) esterification, (ii) isomerization, (iii) Diels-Alder cycloaddition, and (iv) dehydrogenation. However, significant challenges arise when designing catalyst materials suitable for process relevant upgrading of bioderived muconic acid; these include isomerization catalyst recyclability and development of robust catalytic materials for Diels-Alder cycloadditions with sterically hindered addends. This talk covers recent efforts to address these issues through integrated computational and experimental investigations. For the isomerization of cis,cis to trans,trans-dimethyl muconate, we provide insight into the mechanism of molecular iodine photocatalysis and catalyst recyclability via product crystallization and separation. Additionally, efforts are discussed toward Diels-Alder cycloaddition of trans,trans-dimethyl muconate with C2+ alkenes toward the production of dimethyl terephthalate and functional alternatives.

Catalytic conversion of bioderived muconic acid to produce drop-in cyclic monomers and functional alternatives

255th National Meeting (2018)

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