A General and Expedient Synthesis of 5- and 6-Membered Cyclic Carbonates by Palladium-Catalyzed Oxidative Carbonylation of 1,2- and 1,3-Diols

✍ Scribed by Prof. Dr. Bartolo Gabriele; Dr. Raffaella Mancuso; Prof. Giuseppe Salerno; Dr. Lucia Veltri; Prof. Mirco Costa; Prof. Dr. Angela Dibenedetto

• Publisher: Wiley (John Wiley & Sons)
• Year: 2011
• Tongue: English
• Weight: 413 KB
• Volume: 4
• Category: Article
• ISSN: 1864-5631
• DOI: 10.1002/cssc.201100250

✦ Synopsis

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.