Conversion of Isosorbide Diacetate to 1,6-Diacetoxyhexane by a Combined Hetero-/Homogeneous Tandem Catalyst System

• Published in: ACS catalysis 2023-09, Vol.13 (17), p.11323-11338
• Main Authors: Slater-Eddy, Gabriel Hart, England, Aidan E., Lima, Diana Quintão, da Cunha, Igor Tadeu, Stones, Maryanne K., Earnden, Laura I., Montoya Pareja, Juan Sebastian, Skinner, Kareem, Soldatov, Dmitriy V., van der Zalm, Joshua, Schlaf, Marcel
• Format: Article
• Language: English
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.3c02708

The combination of Ru/C with La­(OTf)3 as the activating Lewis acid and dimethylsulfone (DMS) as a modifier in HOAc solvent enables the conversion of the glucose derivative isosorbide diacetate (2,5-di-O-acetyl-1,4:3,6-dianhydro-d-glucitol) to 1,6-diacetoxyhexane (hexane-1,6-diyl diacetate) in up to 22% yield with a blend of alkanes as side-products resulting from total hydrodeoxygenation (HDO) of the substrate. Serendipitously, the use of DMS added as an internal standard and initially assumed to be inert led to the modification of the catalyst, effecting attenuated catalyst system activity and thus higher selectivity. This allows for the persistence of the partially deoxygenated desired acetylated α,ω-diol product in the reaction mixture. SEM-EDS and XPS analyses of the recovered catalyst showed that the modification consists of a concomitant deposition of La3+ and sulfur on the catalyst surface.