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 1-menthol employing asymmetric catalysts.
Continuing efforts have been devoted to the exploration of new catalytic reactions using new BINAPmetal complexes and their applications to industrial asymmetric synthesis. Among them, asymmetric hydrogenation of functionalyzed olefins and ketones by use of BINAP-ruthenium (II) complexes provides 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.
