Catalytic Diene-Diol Benzannulation for Polycyclic Aromatic Hydrocarbon Construction

University Of Texas At Austin, Austin TX

Investigators

Abstract

The Chemical Synthesis Program of the NSF Chemistry Division supports the research of Professor Michael J. Krische in the Department of Chemistry at the University of Texas at Austin. Professor Krische and his students are developing novel, green catalytic methods for the construction of PAH (polycyclic aromatic hydrocarbon) - materials that are used broadly in molecular electronics. Professor Krische's method involves the byproduct-free coupling of inexpensive, abundant petrochemical feedstocks (dienes) with a renewable feedstock (diols). PAH materials are formed upon dehydration of the reaction products, meaning water is the only chemical byproduct. This project lies at the interface of organic, organometallic and materials chemistry and provides a suitable forum for the education of undergraduate, graduate and postdoctoral scientists. With the growing Hispanic demographic in Texas, Professor Krische's group has played a strong role in the education and training of students from groups historically underrepresented in science. Outreach activities include an annual research symposia sponsored by the Center for Green Chemistry and Catalysis led by Professor Krische, which features lectures by leading chemists in the field of catalysis, as well as poster sessions hosting undergraduate, graduate and postdoctoral scientists. The Krische laboratory is pioneering a broad, new class of catalytic carbon-carbon (C-C) bond formations that merge the characteristics of catalytic hydrogenation and carbonyl addition, representing the first "C-C bond forming hydrogenations" beyond hydroformylation. This new pattern of reactivity is the basis of a ruthenium(0) catalyzed diene-diol [4+2] cycloaddition. This byproduct-free transformation is being used to advance new benzannulation technology for the construction of Polycyclic Aromatic Hydrocarbons (PAHs). Acenes, polyphenylenes, fluoranthenes and carbon nano-allotropes - there is great interest in such PAH materials in the field of molecular electronics. However, since the advent of biaryl cross-coupling technology, the field of PAH construction has remained largely unchanged. Just as biaryl cross-coupling technology revolutionized PAH construction, diene-diol benzannulation may unlock new PAH chemical space, broadly impacting research across the carbon nano-allotrope and molecular device communities. The educational plan includes annual research symposia sponsored by the Center for Green Chemistry and Catalysis led by Professor Krische, which features lectures by leading chemists in the field of catalysis, as well as poster sessions hosting undergraduate, graduate and postdoctoral scientists.