title: A general and expedient synthesis of 5- and 6-membered cyclic carbonates by palladium-catalyzed oxidative carbonylation of 1,2- and 1,3-diols.
abstract: We present a general, practical, and efficient approach to 5- and 6-membered organic carbonates by palladium-catalyzed direct oxidative carbonylation of 1,2- and 1,3-diols, respectively. Reactions were carried out at 100 °C in N,N-dimethylacetamide as the solvent under 20 atm (at 25 °C; 1 atm=101.3 kPa) of a 4:1 v/v CO/air mixture in the presence of 0.5-2 mol % of PdI(2) and KI (KI/PdI(2) molar ratio=10). Excess dehydrating agent, such as trimethyl orthoacetate, was necessary in several cases to obtain appreciable results. The method could also be applied to the synthesis of a high-value-added glycerol carbonate from glycerol, a readily available raw material. When applied to α-D-glucose, a double carbonylation process took place, with direct formation of α-D-glucofuranose 1,2:5,6-dicarbonate.
authors.affiliation: Dipartimento di Scienze Farmaceutiche, Università della Calabria, 87036 Arcavacata di Rende (CS), Italy. b.gabriele@unical.it
authors.forename: Bartolo
authors.initials: B
authors.lastname: Gabriele
authors.forename: Raffaella
authors.initials: R
authors.lastname: Mancuso
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Salerno
authors.forename: Lucia
authors.initials: L
authors.lastname: Veltri
authors.forename: Mirco
authors.initials: M
authors.lastname: Costa
authors.forename: Angela
authors.initials: A
authors.lastname: Dibenedetto
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry; D002254:Carbonates / Q000138:chemical synthesis*; D002384:Catalysis; D003500:Cyclization; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*
chemical_list: D002254:Carbonates; D010165:Palladium; D002248:Carbon Monoxide; D010100:Oxygen