From Prochiral N-Heterocyclic Carbenes to Optically Pure Metal Complexes New Opportunities in Asymmetric Catalysis

Lingyu Kong (1) , Jennifer Morvan (2) , Delphine Pichon (2) , Marion Jean (1) , Muriel Albalat (1) , Thomas Vives (2) , Sophie Colombel-Rouen (2) , Michel Giorgi (3, 4) , Vincent Dorcet (2) , Thierry Roisnel (2) , Christophe Crévisy (2) , Didier Nuel (1) , Paola Nava (1) , Stéphane Humbel (1) , Nicolas Vanthuyne (1) , Marc Mauduit (2) , Hervé Clavier (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille
2 ISCR - Institut des Sciences Chimiques de Rennes
3 FSCM - Fédération Sciences Chimiques Marseille
4 AMU - Aix Marseille Université

Well-defined optically pure transition metal (TM) complexes bearing C- and C-symmetric N-heterocyclic carbene (NHC) ligands were prepared from prochiral NHC precursors. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces an axis of chirality. Configurationally stable atropisomers of various NHC-containing TM complexes were isolated by preparative HPLC on a chiral stationary phase in good yields and excellent optical purities (up to 99.5% ee). The carbene transfer from an optically pure Cu complex to a gold or palladium center reveals, for the first time, a full stereoretentivity, supporting the hypothesis of an associative mechanism for the transmetalation. The potential of these new chiral TM complexes was illustrated in asymmetric catalysis with up to 98% ee.

Domains: Chemical Sciences; Coordination chemistry; Chemical Sciences; Catalysis

Lingyu Kong, Jennifer Morvan, Delphine Pichon, Marion Jean, Muriel Albalat, et al.. From Prochiral N-Heterocyclic Carbenes to Optically Pure Metal Complexes New Opportunities in Asymmetric Catalysis. Journal of the American Chemical Society, 2020, 142 (1), pp.93-98. ⟨10.1021/jacs.9b12698⟩. ⟨hal-02442228⟩