Unprecedented cooperative DBU-CuCl2 catalysis for the incorporation of carbon dioxide into homopropargylic amines leading to 6-methylene-1,3-oxazin-2-ones
| Autor: | Ida Ziccarelli, Nicola Della Ca, Corrado Cuocci, Raffaella Mancuso, Carla Carfagna, Christian Silvio Pomelli, Bartolo Gabriele, Diego Olivieri |
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| Přispěvatelé: | Mancuso R., Ziccarelli I., Pomelli C.S., Cuocci C., Della Ca' N., Olivieri D., Carfagna C., Gabriele B. |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Cooperative catalysi
010405 organic chemistry Chemistry Substrate (chemistry) 010402 general chemistry Triple bond 01 natural sciences Combinatorial chemistry Catalysis 0104 chemical sciences Oxazinones chemistry.chemical_compound Deprotonation Carboxylation Cyclization Intramolecular force Cooperative catalysis Copper Protonolysis Physical and Theoretical Chemistry Methylene |
| Popis: | We report the first example of cooperative catalysis by DBU and CuCl2, which allows the carboxylation of homopropargylic amines to high value added 6-methylene-1,3-oxazin-2-ones. This reaction also represents the first efficient method for the catalytic incorporation of CO2 into an acyclic substrate to give oxazinones. DFT calculations are in agreement with a mechanism involving: a) deprotonation of the substrate by DBU; b) CO2 capture with formation of a copper carbamate; c) 6-exo-dig cyclization through intramolecular triple bond insertion; and d) protonolysis, with regeneration of DBU and CuCl2 catalysts. The structure of a representative product has been confirmed by XDR analysis. |
| Databáze: | OpenAIRE |
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