Biofuels have been gaining popularity as an alternative to petroleum based fuels in response to increased regulation of greenhouse gas emissions and decreasing global production of crude oil. At LANL, we are developing a route from biomass to biofuels that encompasses dehydration of sugars followed by carbon chain extension to furans. For this project, a computational study was performed to help explain the diverse reactivity patterns of these furans during acid catalysis. In particular, we have developed a protocol for calculating pKas of the protonated furan substrates based on a thermodynamic cycle. After discussing the challenges encountered while developing this protocol, we protonate each furan substrate at various sites and calculate the resulting pKas to determine the preferred site (most basic) of protonation. Finally, we show that the nature of the most basic site of each substrate adequately explains its behavior (ring opening, decomposition, or no reaction) during acid catalysis.

Protonation of biomass-derived substrates: A computational challenge

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.