Improved synthesis of Bn5CpRu(CO)(2)Cl and its application as racemization catalyst in preparative-scale metalloenzymatic dynamic kinetic resolution of 1-phenylethanol

• Published in: Pure and Applied Chemistry
• Main Authors: Mavrynsky, Denys, Kanerva, LT, Sillanpaa, R, Leino, Reko
• Format: Article in Journal/Newspaper
• Language: unknown
• Published: 2011
• Subjects: chemoenzymatic synthesis; cyclopentadienyl; dynamic kinetic resolution (DKR); Novozym; ruthenium; Antarc*; Antarctica
• Online Access: https://research.abo.fi/en/publications/0cdeb2e9-29c0-4d61-beb3-3f95ce502d5b; https://doi.org/10.1351/PAC-CON-10-09-05

An improved gram-scale synthesis of Bn5CpRu(CO)(2)Cl is reported based on heating of pentabenzylcyclopentadiene with Ru-3(CO)(12) at 160 degrees C under argon atmosphere in mesitylene followed by addition of chloroform, continued heating, and evaporation of the solvents. Subsequent washing of unreacted ligand precursor with hexane provided pure title compound in 77 % yield. In combination with Candida antarctica lipase B (CAL-B) (Novozym 435), this complex forms a highly active racemization catalyst for metallo enzymatic dynamic kinetic resolution (DKR) of secondary alcohols as demonstrated in the present work by converting 100 g of racemic 1-phenylethanol to (R)-1-phenylethanol in > 99 % ee and 93 % overall yield over two steps using 0.05 mol % loading of the metal catalyst and 1 mass % loading of immobilized enzyme. In addition, the synthesis and crystallographic characterization of the palladium congener Bn5CpPd(PPh3)Cl are briefly discussed.