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

doi:10.1071/CH16206

RESEARCH FRONT

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Mechanistic Insights into Water-Catalyzed Formation of Levoglucosenone from Anhydrosugar Intermediates by Means of High-Level Theoretical Procedures

Wenchao Wan ^A , Li-Juan Yu ^A and Amir Karton ^A ^B

+ Author Affiliations

- Author Affiliations

^A School of Chemistry and Biochemistry, The University of Western Australia, Perth, WA 6009, Australia.

^B Corresponding author. Email: amir.karton@uwa.edu.au

Australian Journal of Chemistry 69(9) 943-949 https://doi.org/10.1071/CH16206
Submitted: 30 March 2016 Accepted: 21 April 2016 Published: 24 May 2016

Abstract

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-α-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 (ΔG^‡₂₉₈ = 68.6 kcal 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 15.1 kcal mol^–1, and the hydration step becomes the rate-determining step with an activation energy of ΔG^‡₂₉₈ = 58.1 kcal mol^–1.

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Mechanistic Insights into Water-Catalyzed Formation of Levoglucosenone from Anhydrosugar Intermediates by Means of High-Level Theoretical Procedures

Abstract

References

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