Asymmetric Transfer Hydrogenation of (Hetero)arylketones with Tethered Rh(III)–N-(p-Tolylsulfonyl)-1,2-diphenylethylene-1,2-diamine Complexes: Scope and Limitations

5 years ago

Asymmetric Transfer Hydrogenation of (Hetero)arylketones with Tethered Rh(III)–N-(p-Tolylsulfonyl)-1,2-diphenylethylene-1,2-diamine Complexes: Scope and Limitations

Charlène Férard, Long-Sheng Zheng, Quentin Llopis, Pierre-Georges Echeverria, Virginie Ratovelomanana-Vidal, Gérard Guillamot, Phannarath Phansavath

A series of new tethered Rh(III)/Cp* complexes containing the N-(p-tolylsulfonyl)-1,2-diphenylethylene-1,2-diamine ligand have been prepared, characterized, and evaluated in the asymmetric transfer hydrogenation (ATH) of a wide range of (hetero)aryl ketones. The reaction was performed under mild conditions with the formic acid/triethylamine (5:2) system as the hydrogen source and provided enantiomerically enriched alcohols with good yields and high to excellent enantioselectivities. Although the nature of the substituents on the phenyl tethering ring did not alter the stereochemical outcome of the reaction, complexes bearing electron-donating groups exhibited a higher catalytic activity than those having electron-withdrawing groups. A scale-up of the ATH of 4-chromanone to the gram scale quantitatively delivered the reduced product with excellent enantioselectivity, demonstrating the potential usefulness of these new complexes.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00436

DOI: 10.1021/acs.joc.7b00436