Mechanistic Insights into the Conversion of Biorenewable Levoglucosanol to Dideoxysugars

Zhou, Mingxia; Krishna, Siddarth H.; De bruyn, Mario; Weckhuysen, Bert M.; Curtiss, Larry A.; Dumesic, James A.; Huber, George W.; Assary, Rajeev S.

doi:10.1021/acssuschemeng.0c06315

Mechanistic Insights into the Conversion of Biorenewable Levoglucosanol to Dideoxysugars

Journal Article · Thu Oct 22 00:00:00 EDT 2020 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.0c06315· OSTI ID:1765536

^[1]; Krishna, Siddarth H. ^[2]; ^[3]; ^[3]; ^[1]; ^[2]; ^[2]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Wisconsin, Madison, WI (United States)
Utrecht University (Netherlands)

Here, a molecular understanding of the conversion of biorenewable threo- and erythro-levoglucosanol (LGOL) to 3,4-dideoxysugars in aqueous medium is provided based on first-principles simulations. The synthetic importance of this transformation is that these intermediates can be quantitatively hydrogenated to (S,S)/(S,R) hexane-1,2,5,6-tetrol (tetrol), whose stereochemistry depends on which dideoxy sugar intermediates are formed during LGOL conversion. The thermodynamic and kinetic feasibility of the acetal (R₂C(OR)₂) hydrolysis in LGOL is investigated via computing the free energy profile. In aqueous medium, the rate-determining step of LGOL hydrolysis is the protonation of the anhydro-bridge oxygen atom of LGOL concurrent with ring opening, yielding the cyclic forms of 3,4-dideoxymannose (DDM) and 3,4-dideoxyglucose (DDG) from threo- and erythro-LGOL, respectively. The measured activation energies of LGOL hydrolysis are 20.5 and 23.6 kcal/mol for DDM and DDG formation, respectively. These values are in agreement with the computed protonation free energies of 17.1 and 18.2 kcal/mol, respectively. Based on the simulations, a Bronsted base-catalyzed isomerization from DDG or DDM to 3,4-dideoxy fructose (DDF) is preferred with lower apparent activation free energy barriers compared to the acid-catalyzed isomerization. In summary, this study provides mechanistic information about the conversion of the biomass-derived anhydro-sugar LGOL to 3,4-dideoxy sugars, which are precursors to renewable high-value chemicals.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Laboratory Computing Resource Center (LCRC) and Center for Nanoscale Materials (CNM)

Sponsoring Organization:: European Union’s Horizon 2020; National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1765536

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 43 Vol. 8; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Mechanistic Insights into the Conversion of Biorenewable Levoglucosanol to Dideoxysugars

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