Critical Influence of 5-Hydroxymethylfurfural Aging and Decomposition on the Utility of Biomass Conversion in Organic Synthesis

Konstantin I Galkin; Elena A Krivodaeva; Leonid V Romashov; Sergey S Zalesskiy; Vadim V Kachala; Julia V Burykina; Valentine P Ananikov

doi:10.1002/anie.201602883

Critical Influence of 5-Hydroxymethylfurfural Aging and Decomposition on the Utility of Biomass Conversion in Organic Synthesis

Angew Chem Int Ed Engl. 2016 Jul 11;55(29):8338-42. doi: 10.1002/anie.201602883. Epub 2016 Jun 8.

Authors

Konstantin I Galkin¹, Elena A Krivodaeva¹, Leonid V Romashov¹, Sergey S Zalesskiy¹, Vadim V Kachala¹, Julia V Burykina¹, Valentine P Ananikov²

Affiliations

¹ Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt, 47, Moscow, 119991, Russia.
² Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt, 47, Moscow, 119991, Russia. val@ioc.ac.ru.

PMID: 27271823
DOI: 10.1002/anie.201602883

Abstract

Spectral studies revealed the presence of a specific arrangement of 5-hydroxymethylfurfural (5-HMF) molecules in solution as a result of a hydrogen-bonding network, and this arrangement readily facilitates the aging of 5-HMF. Deterioration of the quality of this platform chemical limits its practical applications, especially in synthesis/pharma areas. The model drug Ranitidine (Zantac®) was synthesized with only 15 % yield starting from 5-HMF which was isolated and stored as an oil after a biomass conversion process. In contrast, a much higher yield of 65 % was obtained by using 5-HMF isolated in crystalline state from an optimized biomass conversion process. The molecular mechanisms responsible for 5-HMF decomposition in solution were established by NMR and ESI-MS studies. A highly selective synthesis of a 5-HMF derivative from glucose was achieved using a protecting group at O(6) position.

Keywords: NMR spectroscopy; biomass; carbohydrates; hydrogen bonds; ionic liquids.

Publication types

Research Support, Non-U.S. Gov't