Abstract: | (S)‐3‐Hydroxy‐2‐methylpropionate, known as the Roche ester, and several of its derivatives were successfully synthesized through asymmetric rhodium‐catalyzed hydrogenation, using INDOLPHOS (diisopropyl{1‐(S)‐3,5‐dioxa‐4‐phosphacyclohepta2,1‐a;3,4‐a′]dinaphthalen‐4‐yl]‐3‐methyl‐2‐indolyl}phosphine) as the chiral ligand, in excellent yield and the highest ee reported up to now (TOF over 5500 h?1 at 25 °C; up to 98% ee at ?40 °C). |