Asymmetric reduction of 2-chloro-3-oxo esters was achieved by catalytic transfer hydrogenation using [RuCl 2 (p-cymene)](S,S)-TsDPEN as the chiral catalyst and HCOOH-Et 3 N as the hydrogen source. Moderate to good yields (up to 85%) and good enantioselectivities (up to 98% ee) were obtained.
The dynamic kinetic resolution of 2-aroyl-1-tetralones was achieved via asymmetric transfer hydrogenation using (S,S)-RuCl(p-cymene)TsDPEN (TsDPEN = N-(tosyl)-1,2-diphenylethylenediamine) in formic acid/triethylamine (5∶2, molar ratio), afforded the desired products in good yields (up to 85%) with diastereomeric ratio up to >99∶1 and high enantiomeric excesses (up to >99%). The absolute configuration of major the product was confirmed by X-ray crystal structure analysis.
A series of new highly efficient chiral aliphatic-aromatic diamine catalysts have been designed and successfully applied to the asymmetric Michael addition of cyclohexanone with nitroolefins under solvent-free conditions without any acidic additives. The desired adducts were obtained in high yields with excellent enantio- and diastereoselectivities of syn products (up to >99% ee, >99:1 dr).
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