Asymmetric O–H insertion reaction of carbenoids catalyzed by chiral bicyclo bisoxazoline copper(I) and (II) complexes

P. Le Maux (1) , D. Carrié (1) , P. Jéhan (2) , G. Simonneaux (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 CRMPO - Centre Régional de Mesures Physiques de l'Ouest

Chiral copper(I) and (II)-bicyclobisoxazoline complexes were found to catalyze the insertion of α-diazocarbonyl compounds into O–H bonds of alcohols. The insertion reactions of various α-diazopropionates proceeded with moderate yields (40–90%) and high enantioselectivities (up to 92% and 94% with copper(I) and copper(II)-catalysts, respectively). A predominant effect on the enantiocontrol of the reaction was observed when copper(I) and (II)-catalysts were associated with NaBARF and molecular sieves (4 Å). © 2016 Elsevier Ltd

Keywords: OeH insertion catalysis; Copper; Chiral bisoxazoline; Enantioselectivity

Domains: Chemical Sciences; Chemical Sciences; Material chemistry

P. Le Maux, D. Carrié, P. Jéhan, G. Simonneaux. Asymmetric O–H insertion reaction of carbenoids catalyzed by chiral bicyclo bisoxazoline copper(I) and (II) complexes. Tetrahedron, 2016, 72 (31), pp.4671--4675. ⟨10.1016/j.tet.2016.06.044⟩. ⟨hal-01367241⟩