0000000000984787
AUTHOR
Benjamin Schäffner
Asymmetric Hydrogenation of Nonfunctionalized Olefins in Propylene Carbonate—Kinetic or Thermodynamic Control?
Iridium-catalyzed hydrogenations of nonfunctionalized olefins in propylene carbonate as the solvent allow efficient catalysis with much higher enantioselectivities in comparison with dichloromethane which is usually employed for these reactions. Experimental and computational studies of the hydrogenation of 1-methylene-1,2,3,4-tetrahydronaphthalene have been performed to understand the limitation for this reaction.
Organic carbonates as alternative solvents for asymmetric hydrogenation
Organic carbonates like propylene carbonate (PC) or butylene carbonate (BC) belong to the class of aprotic, highly dipolar solvents (AHD). Interestingly, their potential as solvents for asymmetric catalysis has been overlooked for a long time. The aim of this work is to evaluate organic carbonates and other organic solvents like THF, CH2Cl2, and acetonitrile as well as members of the AHD-family (DMF, DMSO, etc.) as media for homogeneous asymmetric hydrogenation. For this reason cationic Rh-complexes based on chiral phosphine ligands were tested in the hydrogenation of typical benchmark substrates. In several trials, significant advantages of organic carbonates were found. In contrast to DMS…