Asymmetric Catalysis in Liquid Confinement: Probing the Performance of Novel Chiral Rhodium–Diene Complexes in Microemulsions and Conventional Solvents
Abstract 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)22 and chiral diene ligands as benchmark reaction. To get access to Rh complexes of different polarity, enantiomerically pure C2-symmetric p-substituted 3,6-diphenylbicyclo3.3.0octadienes 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.
%0 Journal Article
%1 doi:10.1002/chem.201900947
%A Deimling, Max
%A Kirchhof, Manuel
%A Schwager, Barbara
%A Qawasmi, Yaseen
%A Savin, Alex
%A Mühlhäuser, Tina
%A Frey, Wolfgang
%A Claasen, Birgit
%A Baro, Angelika
%A Sottmann, Thomas
%A Laschat, Sabine
%D 2019
%J Chemistry – A European Journal
%K Qawasmi Sottmann
%P 9464-9476
%R 10.1002/chem.201900947
%T Asymmetric Catalysis in Liquid Confinement: Probing the Performance of Novel Chiral Rhodium–Diene Complexes in Microemulsions and Conventional Solvents
%U https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201900947
%V 25
%X Abstract 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)22 and chiral diene ligands as benchmark reaction. To get access to Rh complexes of different polarity, enantiomerically pure C2-symmetric p-substituted 3,6-diphenylbicyclo3.3.0octadienes 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.
@article{doi:10.1002/chem.201900947,
abstract = {Abstract 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-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 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.},
added-at = {2019-06-25T14:03:28.000+0200},
author = {Deimling, Max and Kirchhof, Manuel and Schwager, Barbara and Qawasmi, Yaseen and Savin, Alex and Mühlhäuser, Tina and Frey, Wolfgang and Claasen, Birgit and Baro, Angelika and Sottmann, Thomas and Laschat, Sabine},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2647dc31cb0e751c703e702e3ad08d7fa/yaseenqawasmi},
doi = {10.1002/chem.201900947},
eprint = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201900947},
interhash = {39cc5e2aa93e07d6a9143bd9372cde34},
intrahash = {647dc31cb0e751c703e702e3ad08d7fa},
journal = {Chemistry – A European Journal},
keywords = {Qawasmi Sottmann},
pages = {9464-9476},
timestamp = {2019-08-07T15:18:05.000+0200},
title = {Asymmetric Catalysis in Liquid Confinement: Probing the Performance of Novel Chiral Rhodium–Diene Complexes in Microemulsions and Conventional Solvents},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201900947},
volume = 25,
year = {2019 }
}
