DBU-promoted nucleophilic activation of organic carbonates

• Published in: European Journal of Organic Chemistry
• Main Authors: Carafa M, MESTO, ERNESTO, QUARANTA, Eugenio
• Other Authors: Carafa, M, Mesto, Ernesto, Quaranta, Eugenio
• Format: Article in Journal/Newspaper
• Language: English
• Published: 2011
• Subjects: Organocatalysis; reaction mechanism; amidine base; carbonic acid ester; Ketene; Carbonic acid
• Online Access: http://hdl.handle.net/11586/134411; https://doi.org/10.1002/ejoc.201001725; http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201001725/pdf

The reactivity of carbonic acid diesters in the presence of the amidine base DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) has been investigated for the first time. Organic carbonates can be activated by DBU through the formation of N-alkoxycarbonyl ketene aminal 2 as the ultimate product. The latter species may form through deprotonation of the corresponding N-alkoxycarbonyl-amidinium cation 1+ by the amidine base. We have for the first time isolated and characterized both in the solid state (X-ray crystal structure determination, IR) and in solution (NMR), a few 1+ chloride salts and studied their reactivity towards the organic base. The reactivity of both 1+ and 2 with methanol has also been explored. Ketene aminal 2 behaves as a “CO2R” carrier, as it can selectively transfer the alkoxycarbonyl group to the alcohol and regenerate the amidine base.