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.
Unprecedented cooperative DBU-CuCl2 catalysis for the incorporation of carbon dioxide into homopropargylic amines leading to 6-methylene-1,3-oxazin-2-ones / Mancuso, R.; Ziccarelli, I.; Pomelli, C. S.; Cuocci, C.; Della Ca', N.; Olivieri, D.; Carfagna, C.; Gabriele, B.. - In: JOURNAL OF CATALYSIS. - ISSN 0021-9517. - 387:(2020), pp. 145-153. [10.1016/j.jcat.2020.03.033]
Unprecedented cooperative DBU-CuCl2 catalysis for the incorporation of carbon dioxide into homopropargylic amines leading to 6-methylene-1,3-oxazin-2-ones
Della Ca' N.;
2020-01-01
Abstract
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.File | Dimensione | Formato | |
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