Rh(I)-Catalyzed Enantioselective Arylation of Cyclic N-Sulfonyl Diketimines Using Planar-Chiral Phosphine-Olefin Ligands Based on a (Cyclopentadienyl)manganese(I) Scaffold with a Highly Fluorinated Aryl Phosphino Group.

Abstract

Catalytic enantioselective 1,2-addition reactions of arylboronic acids with 1,2,5-thiadiazoline 1,1-dioxide derivatives were achieved using planar-chiral phosphine-olefin ligand L5 with a bis[(2,3,4,5,6-pentafluoro)phenyl]phosphino group, showing ≤98% ee. The enantioselectivities of the addition products were improved by increasing the number of fluoro substituents on the aromatic ring of the ligand. X-ray crystallographic studies of 3aa and [RhCl/L5]2 revealed the absolute configuration of the enantioenriched addition product 3 and the mode of phosphine-olefin bidentate coordination of L5 to a rhodium(I) cation.