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(C2 H4 )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-diphenylbicyclo[3.3.0]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 H2 O/KOH and toluene/reactants was formulated using the hydrophilic sugar surfactant n-octyl β-d-glucopyranoside (C8 G1 ) 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.
Keywords: C−C coupling; asymmetric catalysis; diene ligands; kinetics; sugar surfactants.
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.