Asymmetric transfer hydrogenation of α,β-unsaturated, α-tosyloxy and α-substituted ketones

Abstract Asymmetric transfer hydrogenation of cyclic and acyclic α,β-unsaturated ketones catalysed by η 6 - p -cymene/ruthenium(II) and η 5 -pentamethylcyclopentadienyl/rhodium(III) complexes have been investigated. Cyclic α,β-unsaturated ketones appeared to be more suitable substrates for the synthesis of enantiomerically pure allylic alcohols than do acyclic α,β-unsaturated ketones. A proposed mechanism for the formation of 4-phenyl-[1,3]-dioxolan-2-one from α-tosyloxy- and halo-substituted acetophenones is discussed. The results of further investigations into the reduction of a range of α-tosyloxyacetophenones and the dynamic kinetic resolution of α-substituted ketones is presented.