Sulfoxidation inside a C 3 -Vanadium(V) Bowl-Shaped Catalyst

Dawei Zhang (1) , Jean-Pierre Dutasta (1) , Véronique Dufaud (2) , Laure Guy (1) , Alexandre Martinez (3)

1 LC - Laboratoire de Chimie - UMR5182
2 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265
3 ISM2 - Institut des Sciences Moléculaires de Marseille

The confined enantiopure oxido-vanadium complex SSS-RRR-1 was synthesized and tested as a catalyst for the oxidation of sulfides into sulfoxides. This catalyst is very efficient with a reaction rate more than 300 times higher than that of the model compound SSS-RRR-3, and a turnover number (TON) close to 10 5 was reached in combination with a good selectivity (more than 90%) in the sulfoxide product. Moreover, enantiomerically enriched sulfoxide can be obtained, breaking through the major limitation of the previous chiral vanatrane catalysts that show no detectable enantiomeric excess (ee). Further investigations revealed that the complex SSS-RRR-1 adopts a bowl-shaped structure with an open hydrophobic pocket. The microenvironment of the chiral pocket above the metal center accounts for the strong improvement in catalytic activity and enantioselectivity.

Mots clés: sulfoxidation; enantioselectivity; supramolecular catalysis; oxido-vanadium complex; high TON; chiral pocket

Domaines: Chimie

Dawei Zhang, Jean-Pierre Dutasta, Véronique Dufaud, Laure Guy, Alexandre Martinez. Sulfoxidation inside a C 3 -Vanadium(V) Bowl-Shaped Catalyst. ACS Catalysis, 2017, 7 (10), pp.7340 - 7345. ⟨10.1021/acscatal.7b01886⟩. ⟨hal-01682776⟩