An
improved synthesis of (S)-ketamine (esketamine)
has been developed, which was cost-effective, and the undesired isomer
could be recovered by racemization. Critical process parameters of
each step were identified as well as the process-related impurities.
The formation mechanisms and control strategies of most impurities
were first discussed. Moreover, the (S)-ketamine
tartrate is a dihydrate, which was disclosed for the first time. The
practicable racemization catalyzed by aluminum chloride was carried
out in quantitative yield with 99% purity. The ICH-grade quality (S)-ketamine hydrochloride was obtained in 51.1% overall
yield (14.0% without racemization) by chiral resolution with three
times recycling of the mother liquors. The robust process of esketamine
could be industrially scalable.