title: Palladium/Carbon dioxide cooperative catalysis for the production of diketone derivatives from carbohydrates.
abstract: The one-pot production of industrially valuable diketone derivatives from carbohydrates is achieved through a bifunctional catalytic process. In particular, Pd/C-catalyzed hydrogenation of HMF in water and under CO2 affords 1-hydroxypentane-2,5-dione with up to 77% yield. The process is also eligible starting from fructose and inulin, affording 1-hydroxyhexane-2,5-dione with 36% and 15% yield, respectively. The key of the process is reversible in situ formation of carbonic acid, which is capable of assisting Pd/C during the hydrogenation reaction by promoting the dehydration of carbohydrates and the ring-opening of furanic intermediates. Interestingly, by changing the reaction medium from H2 O to a H2 O/THF mixture (1:9), it is possible to switch the selectivity of the reaction and to produce 2,5-hexanadione with 83% yield. Within the framework of sustainable chemistry, reactions presented in this report show 100% carbon economy, involve CO2 to generate acidity, require water as a solvent, and are conducted under rather low hydrogen pressures (10 bar).
authors: Institut de Chimie des Milieux et Matériaux de Poitiers, CNRS/Université de Poitiers, 1 rue marcel Doré, 86022 Poitiers (France).
authors: Fei
authors: F
authors: Liu
authors: Maïté
authors: M
authors: Audemar
authors: Karine
authors: K
authors: De Oliveira Vigier
authors: Jean-Marc
authors: JM
authors: Clacens
authors: Floryan
authors: F
authors: De Campo
authors: François
authors: F
authors: Jérôme
mesh_terms: D002241:Carbohydrates / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D006865:Hydrogenation; D007659:Ketones / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D011312:Pressure; D014867:Water / Q000737:chemistry
chemical_list: D002241:Carbohydrates; D007659:Ketones; D014867:Water; D002245:Carbon Dioxide; D010165:Palladium
keywords: biomass; carbon dioxide; diketones; furanes; heterogeneous catalysis