title: Catalytic Coupling of Carbon Dioxide with Terpene Scaffolds: Access to Challenging Bio-Based Organic Carbonates.
abstract: The challenging coupling of highly substituted terpene oxides and carbon dioxide into bio-based cyclic organic carbonates catalyzed by Al(aminotriphenolate) complexes is reported. Both acyclic as well as cyclic terpene oxides were used as coupling partners, showing distinct reactivity/selectivity behavior. Whereas cyclic terpene oxides showed excellent chemoselectivity towards the organic carbonate product, acyclic substrates exhibited poorer selectivities owing to concomitant epoxide rearrangement reactions and the formation of undesired oligo/polyether side products. Considering the challenging nature of these coupling reactions, the isolated yields of the targeted bio-carbonates are reasonable and in most cases in the range 50-60 %. The first crystal structures of tri-substituted terpene based cyclic carbonates are reported and their stereoconnectivity suggests that their formation proceeds through a double inversion pathway.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain. akleij@iciq.es.
authors.forename: Giulia
authors.identifier: 0000-0003-1370-2952
authors.initials: G
authors.lastname: Fiorani
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Moritz
authors.initials: M
authors.lastname: Stuck
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Carmen
authors.initials: C
authors.lastname: Martín
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Marta Martínez
authors.initials: MM
authors.lastname: Belmonte
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Eddy
authors.initials: E
authors.lastname: Martin
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Eduardo C
authors.initials: EC
authors.lastname: Escudero-Adán
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain. gfiorani@iciq.es.|Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, 08010, Barcelona, Spain. gfiorani@iciq.es.
authors.forename: Arjan W
authors.identifier: 0000-0002-7402-4764
authors.initials: AW
authors.lastname: Kleij
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D002384:Catalysis; D005027:Ethylene Oxide / Q000737:chemistry; D013729:Terpenes / Q000737:chemistry*
chemical_list: D002254:Carbonates; D013729:Terpenes; D002245:Carbon Dioxide; D005027:Ethylene Oxide
keywords: aluminium; biocarbonates; carbon dioxide; homogeneous catalysis; terpenes