Chiral Ruthenium-Catalyzed Hydrogenation of β-Keto Sulfoxides

Recent developments in chiral non-racemic sulfinyl group chemistry in asymmetric synthesis

“…In the field of stereoselective hydrogenation of functionalised ketones in the presence of a chiral metal catalyst, the hydrogenation of β-keto sulfoxides catalysed by ruthenium complexes was investigated by Genêt 167 . Starting from either optically pure or racemic β-keto sulfoxides 196, the diastereoselectivity of the hydrogenation was controlled by the chiral ruthenium complexes (Scheme 95).…”

The synthesis of thiols, selenols, sulfides, selenides, sulfoxides, selenoxides, sulfones and selenones

“…153 The ruthenium-catalysed hydrogenation of enantiomerically pure β-keto sulfoxides gives β-hydroxy sulfoxides with only moderate diastereoselectivity. 154 When chiral ruthenium catalysts were used, the diastereoselectivity was much higher and was found to be independent of the stereochemistry at sulfur (Scheme 89). 154 Enantiomerically pure β-keto sulfoxides have been prepared by the addition of the α-sulfinyl anion derived from (R)-methyl p-tolyl sulfoxide to nitriles.…”

“…154 When chiral ruthenium catalysts were used, the diastereoselectivity was much higher and was found to be independent of the stereochemistry at sulfur (Scheme 89). 154 Enantiomerically pure β-keto sulfoxides have been prepared by the addition of the α-sulfinyl anion derived from (R)-methyl p-tolyl sulfoxide to nitriles. 155 The reduction of enantiomerically pure α-sulfinyl ketimines with DIBAL-H and zinc bromide proceeds with essentially complete diastereoselectivity to give syn-β-amino sulfoxides in high yield (Scheme 90).…”

Stereoselective Synthesis of iso-Dolaproine via Dynamic Kinetic Resolution

“…In our continuous interest in ruthenium-catalyzed asymmetric hydrogenation, we have already described several applications of this technology to the synthesis of biologically or industrially relevant molecules . On the basis of previous work on the asymmetric hydrogenation of chiral γ -amino β -keto esters, we decided to investigate the reduction of γ -amino β -keto α -methyl esters derived from ( S )-proline.…”