Asymmetric Catalysis in Liquid Confinement: Probing the Performance of Novel Chiral Rhodium–Diene Complexes in Microemulsions and Conventional Solvents

The role of liquid confinement on the asymmetric Rh catalysis was studied using the 1,2-addition of phenylboroxine ( 2 ) to N-tosylimine 1 in the presence of RhCl(C₂H₄)₂]₂ and chiral diene ligands as benchmark reaction. To get access to Rh complexes of different polarity, enantiomerically pure C₂-symmetric p-substituted 3,6-diphenylbicyclo3.3.0]octadienes 4 and diastereomerically enriched unsymmetric norbornadienes 5 and 6 carrying either the Evans or the SuperQuat auxiliary were synthesized. A microemulsion containing the equal amounts of H₂O/KOH and toluene/reactants was formulated using the hydrophilic sugar surfactant n-octyl β-d -glucopyranoside (C₈G₁) to mediate the miscibility between the nonpolar reactants and KOH, needed to activate the Rh–diene complex. Prominent features of this organized reaction medium are its temperature insensitivity as well as the presence of water and toluene-rich compartments with a domain size of 55 Å confirmed by small-angle X-ray scattering (SAXS). Although bicyclooctadiene ligands 4 a , b , e performed equally well under homogeneous and microemulsion conditions, ligands 4 c , d gave a different chemoselectivity. For norbornadienes 5 , 6 , however, microemulsions markedly improved conversion and enantioselectivity as well as reaction rate, as was confirmed by kinetic studies using ligand 5 b .