Organocatalytic Synthesis of Substituted Vinylene Carbonates

Killian Onida (1) , Alice J Haddleton (2) , Sébastien Norsic (2) , Christophe Boisson (2) , Franck d'Agosto (2) , Nicolas Duguet (1)

1 ICBMS - Institut de Chimie et Biochimie Moléculaires et Supramoléculaires
2 CP2M - Catalyse, Polymérisation, Procédés et Matériaux

The organocatalytic synthesis of substituted vinylene carbonates from benzoins and acyloins was studied using diphenyl carbonate as a carbonyl source. A range of N-Heterocyclic Carbene (NHC) precursors were screened and it was found that imidazolium salts were the most active for this transformation. The reaction occurs at 90 °C under solvent-free conditions. A wide range of substituted vinylene carbonates (symmetrical and unsymmetrical, aromatic or aliphatic), including some derived from natural products, were prepared with 20-99% isolated yields (24 examples). The reaction was also developed using thermomorphic polyethylene-supported organocatalysts as recoverable and recyclable species. The use of such species facilitates the workup and allows the synthesis of vinylene carbonates on the preparative scale (> 30 g after 5 runs).

Mots clés: Vinylene carbonates; Benzoin; Diphenyl carbonate; Organocatalysis; Thermomorphic polyethylene

Domaines: Chimie organique; Catalyse

Killian Onida, Alice J Haddleton, Sébastien Norsic, Christophe Boisson, Franck d'Agosto, et al.. Organocatalytic Synthesis of Substituted Vinylene Carbonates. Advanced Synthesis and Catalysis, 2021, 363 (22), pp.5129-5137. ⟨10.1002/adsc.202100870⟩. ⟨hal-03821278⟩