title: Catalytic deoxydehydration of diols to olefins by using a bulky cyclopentadiene-based trioxorhenium catalyst.
abstract: A bulky cyclopentadienyl (Cp)-based trioxorhenium compound was developed for the catalytic deoxydehydration of vicinal diols to olefins. The 1,2,4-tri(tert-butyl)cyclopentadienyl trioxorhenium (2) catalyst was synthesised in a two-step synthesis procedure. Dirhenium decacarbonyl was converted into 1,2,4-tri(tert-butyl)cyclopentadienyl tricarbonyl rhenium, followed by a biphasic oxidation with H2 O2 . These two new three-legged compounds with a 'piano-stool' configuration were fully characterised, including their single crystal X-ray structures. Deoxydehydration reaction conditions were optimised by using 2 mol % loading of 2 for the conversion of 1,2-octanediol into 1-octene. Different phosphine-based and other, more conventional, reductants were tested in combination with 2. Under optimised conditions, a variety of vicinal diols (aromatic and aliphatic, internal and terminal) were converted into olefins in good to excellent yields, and with minimal olefin isomerisation. A high turnover number of 1400 per Re was achieved for the deoxydehydration of 1,2-octanediol. Furthermore, the biomass-derived polyols (glycerol and erythritol) were converted into their corresponding olefinic products by 2 as the catalyst.
authors.affiliation: Organic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands).
authors.forename: Suresh
authors.initials: S
authors.lastname: Raju
authors.forename: Johann T B H
authors.initials: JT
authors.lastname: Jastrzebski
authors.forename: Martin
authors.initials: M
authors.lastname: Lutz
authors.forename: Robertus J M
authors.initials: RJ
authors.lastname: Klein Gebbink
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003517:Cyclopentanes / Q000737:chemistry*; D006018:Glycols / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D014835:Volatilization
chemical_list: D000475:Alkenes; D003517:Cyclopentanes; D006018:Glycols; D012211:Rhenium; D010100:Oxygen
keywords: biomass; cyclopentadienyl ligands; deoxydehydration; homogeneous catalysis; rhenium