Rhodium-Catalyzed Enantioselective Anti-Markovnikov Hydroformylation of α-Substituted Acryl Acid Derivatives.

Rhodium-catalyzed asymmetric anti-Markovnikov hydroformylation of α-substituted acrylates/acrylamides has been developed. By employing the Rh/(S,S)-DTBM-YanPhos complex, a series of β-chiral linear aldehydes were obtained in high yields (up to 94% yield) and high enantioselectivities (up to 96% ee). The utility of this methodology is demonstrated by a gram-scale reaction and a concise synthetic route to chiral γ-butyrolactone.