Industrial asymmetric synthesis by use of metal-BINAP catalysts

Abstract

This article covers the history and present progress of the industrial asymmetric synthesis by use of BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl)-metal catalysts. Especially, the historic discovery of the BINAP-rhodium ( I )-catalyzed 1,3-hydrogen migration of N,N-diethylgeranylamine (GDEA) and the achievement of practical preparation of optically active BINAP, led to the establishment of the first industrial process for efficient production of l-menthol employing asymmetric catalysts. Continuing efforts have been devoted to the exploration of new catalytic reactions using new BINAP-metal complexes and their applications to industrial asymmetric synthesis. Among them, asymmetric hydrogenation of functionalyzed olefins and ketones by use of BINAP-ruthenium ( II ) complexes pro-vides fruitful results. Today, a wide range of chiral compounds including the pharmaceutical intermediates 4-acetoxy-2-azetidinone (4-AA) and 1,2-propanediol (2-PPD) are produced in industrial scale in Takasago.