Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins

In silico-based optimization of Ir/P,S-catalysts for the asymmetric hydrogenation unfunctionalized olefins using (E)-1-(but-2-en-2-yl)-4-methoxybenzene as a benchmark olefin has been carried out. DFT calculations revealed that thioether group major role in directing coordination. This, together with configuration biphenyl phosphite group, an impact maximizing energy gap between most stable transition states leading to opposite enantiomers. As result, optimized catalyst proved be efficient range alkenes same substitution pattern and geometry olefin, regardless presence functional groups different coordination abilities (ee values up 97%). Appealingly, further modifications at biaryl moiety allowed highly enantioselective patterns (e.g., ?,?-unsaturated lactones lactams, 1,1?-disubstituted enol phosphinates, cyclic ?-enamides; ee >99%).