Mechanistic insights into water-catalyzed formation of levoglucosenone from anhydrosugar intermediates by means of high-level theoretical procedures

Wenchao Wan, Li-Juan Yu, Amir Karton

Research output: Contribution to journalArticle

8 Citations (Scopus)
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Abstract

© CSIRO 2016.
Levoglucosenone (LGO) is an important anhydrosugar product of fast pyrolysis of cellulose and biomass. We use the high-level G4(MP2) thermochemical protocol to study the reaction mechanism for the formation of LGO from the 1,4:3,6-dianhydro-a-d-glucopyranose (DGP) pyrolysis intermediate. We find that the DGP-to-LGO conversion proceeds via a multistep reaction mechanism, which involves ring-opening, ring-closing, enol-to-keto tautomerization, hydration, and dehydration reactions. The rate-determining step for the uncatalyzed process is the enol-to-keto tautomerization (?G‡298=68.6kcal mol-1). We find that a water molecule can catalyze five of the seven steps in the reaction pathway. In the water-catalyzed process, the barrier for the enol-to-keto tautomerization is reduced by as much as 15.1kcal mol-1, and the hydration step becomes the rate-determining step with an activation energy of ?G‡298=58.1kcal mol-1.
Original languageEnglish
Pages (from-to)943-949
JournalAustralian Journal of Chemistry
Volume69
Issue number9
DOIs
Publication statusPublished - 24 May 2016

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