Catalytic Enantioselective Cyclopropanation of α-Fluoroacrylates: An Experimental and Theoretical Study

Amandine Pons (1) , Vincent Tognetti (1) , Laurent Joubert (1) , Thomas Poisson (1) , Xavier Pannecoucke (1) , André Charette (2) , Philippe Jubault (1)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 CCVC - Centre In Green Chemistry and Catalysis [Montréal]

Herein, we report the catalytic asymmetric synthesis of functionalized fluorocyclopropanes from α-fluoroacrylates. The method using Rh2((S)-TCPTTL)4 allowed the difficult reaction of an in situ-generated electrophilic Rh-carbene with an electron-poor α-fluoroacrylate. The desired fluorocyclopropanes were obtained in good yields, excellent dr and ee. Finally, the mechanism of this transformation was studied by density functional theory (DFT) calculations to explain the particular reactivity of the donor–acceptor diazo compounds with electron-deficient α-fluoroacrylates.

Keywords: fluorine; cyclopropanes; rhodium; DFT calculations; asymmetric synthesis

Domains: Chemical Sciences

Amandine Pons, Vincent Tognetti, Laurent Joubert, Thomas Poisson, Xavier Pannecoucke, et al.. Catalytic Enantioselective Cyclopropanation of α-Fluoroacrylates: An Experimental and Theoretical Study. ACS Catalysis, 2019, 9 (3), pp.2594-2598. ⟨10.1021/acscatal.9b00354⟩. ⟨hal-02278764⟩