Investigations into Competitive Cycloaddition/Cyclization or Elimination from 1,1-Dimethyl-propargylcarbamates of Anilines

Régis Delatouche (1) , Aurélien Lesage (1) , Floraine Collette (2) , Valérie Héroguez (2, 3) , Philippe Bertrand (1)

1 SRSN - Synthèse et réactivité des substances naturelles
2 LCPO - Laboratoire de Chimie des Polymères Organiques
3 Team 1 LCPO : Polymerization Catalyses & Engineering

The copper-catalyzed reaction of 1,1-dimethyl-O-propargyl aniline carbamates was studied and revealed the unexpected formation of oxazolidin-2-ones and alkylamines. An in-depth study of the reaction conditions showed that the formation of these products was highly dependent on the solvent, copper catalyst and aniline substituents. The reaction can be oriented towards oxazolidinones in pyridine and alkylamines in ethanol, whereas cycloaddition can be achieved in dry tetrahydrofuran.

Mots clés: CLICK CHEMISTRY; CATALYZED CYCLIZATION; PROPARGYL CARBONATES; CONVENIENT SYNTHESIS; MILD CONDITIONS; ALCOHOLS; 4-METHYLENE-2-OXAZOLIDINONES; ISOCYANATES; AMINES; BOND

Domaines: Polymères

Régis Delatouche, Aurélien Lesage, Floraine Collette, Valérie Héroguez, Philippe Bertrand. Investigations into Competitive Cycloaddition/Cyclization or Elimination from 1,1-Dimethyl-propargylcarbamates of Anilines. Australian Journal of Chemistry, 2011, 64 (2), pp.166-173. ⟨10.1071/CH10344⟩. ⟨hal-00947153⟩