Supramolecularly Regulated Ligands for Asymmetric Hydroformylations and Hydrogenations.

Herein we report the use of polyether binders as regulation agents (RAs) to enhance the enantioselectivity of rhodium-catalyzed transformations. For reactions of diverse substrates mediated by rhodium complexes of the α,ω-bisphosphite-polyether ligands 1-5,a-d, the enantiomeric excess (ee) of hydroformylations was increased by up to 82 % (substrate: vinyl benzoate, 96 % ee), and the ee value of hydrogenations was increased by up to 5 % (substrate: N-(1-(naphthalene-1-yl)vinyl)acetamide, 78 % ee). The ligand design enabled the regulation of enantioselectivity by generation of an array of catalysts that simultaneously preserve the advantages of a privileged structure in asymmetric catalysis and offer geometrically close catalytic sites. The highest enantioselectivities in the hydroformylation of vinyl acetate with ligand 4 b were achieved by using the Rb[B(3,5-(CF3)2 C6 H3)4] (RbBArF) as the RA. The enantioselective hydrogenation of the substrates 10 required the rhodium catalysts derived from bisphosphites 3 a or 4 a, either alone or in combination with different RAs (sodium, cesium, or (R,R)-bis(1-phenylethyl)ammonium salts). This design approach was supported by results from computational studies.