Stereoselective hydrogenation via dynamic kinetic resolution

Recent Advances of BINAP Chemistry in the Industrial Aspects

“…Thus, the hydrogenation of 9 catalyzed by a (-)-41-Ru(II) complex gave (2S,3R)-10 in 98.6% de and 99.4% ee (cf., BINAP, 86% de). 21 The SEGPHOS ligands based on our working hypothesis has been shown the high efficiency in the asymmetric catalytic hydrogenations of a wide variety of carbonyl compounds. Other potentialities and the theoretical studies of the SEGPHOS ligands in asymmetric reactions are now in progress.…”

“…Diastereo-and enantioselective hydrogenation of 2-substituted 3-oxo carboxylic esters was reported in 1989. 21 In the course of our research on asymmetric hydrogenation of various functionalized ketones, we found that DM-BINAP is superior to BINAP in diastereoselective asymmetric hydrogenation of methyl (±)-2-(benzamidomethyl)-3-oxobutanoate [(±)-9], giving syn-(2S,3R)-10 in 91% de (98% ee) and 84% de (97% ee), respectively. 22 This procedure has been successfully applied to the industrial production of a carbapenem key intermediate 11 (Scheme 5) on a scale of 100 tons per year.…”

Access to Enantiopure α‐Alkyl‐β‐hydroxy Esters through Dynamic Kinetic Resolutions Employing Purified/Overexpressed Alcohol Dehydrogenases

“…Historically this transformation has been categorised as a DKRtype process. [7] In fact, the first time where this term was implemented by Noyori, [8] corresponds to a Rucatalysed hydrogenation of α-substituted β-ketoesters. Initial examples of the biocatalysed reduction of these compounds were shown by Deol et al in 1976 employing baker's yeast.…”

Asymmetric Hydrogenation

“…The great utility of this method has been demonstrated in the production of many enantiopure building blocks. A representative example of the production of carbapenems by Takasago International Corporation is shown in Scheme 15 [43,44] …”