Palladium/Carbon Dioxide Cooperative Catalysis for the Production of Diketone Derivatives from Carbohydrates

• Published in: ChemSusChem Vol. 7; no. 8; pp. 2089 - 2093
• Main Authors: Liu, Fei, Audemar, Maïté, De Oliveira Vigier, Karine, Clacens, Jean-Marc, De Campo, Floryan, Jérôme, François
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.08.2014; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: biomass; Carbohydrates; Carbohydrates - chemistry; Carbon dioxide; Carbon Dioxide - chemistry; Catalysis; diketones; furanes; heterogeneous catalysis; Hydrogenation; Ketones - chemistry; Palladium - chemistry; Pressure; Water - chemistry; furanes; carbon dioxide; biomass; diketones; heterogeneous catalysis
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201402221

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 H2O to a H2O/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). Allez les verts! Valuable diketone derivatives are produced from carbohydrates and 5‐hydroxymethylfurfural (HMF) through a flexible cooperative catalysis process involving a palladium/carbon dioxide system. Key to 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.