ABSTRACT
A novel catalytic method for the straightforward hydrogenation of carboxamides and esters to primary alcohols has been developed. Chiral modification in the ligand sphere of the well-defined Cp*Ru catalyst molecule opens up a new possibility for the development of an enantioselective hydrogenation of racemic substrates via dynamic kinetic resolution.
Subject(s)
Amides/chemical synthesis , Amines/chemistry , Esters/chemical synthesis , Organometallic Compounds/chemistry , Ruthenium/chemistry , Amides/chemistry , Catalysis , Crystallography, X-Ray , Esters/chemistry , Hydrogenation , Models, Molecular , Molecular Structure , StereoisomerismABSTRACT
Highly enantioselective hydrogenative desymmetrization of bicyclic imides has been developed with chiral Cp*Ru(PN) catalysts. The present hydrogenation directly provides stereochemically well-defined cyclic compounds with excellent enantiomeric exessses, which might otherwise require a detour to reach.
Subject(s)
Bridged Bicyclo Compounds, Heterocyclic/chemical synthesis , Imides/chemical synthesis , Bridged Bicyclo Compounds, Heterocyclic/chemistry , Hydrogenation , Imides/chemistry , Molecular Structure , StereoisomerismABSTRACT
Awakening of the Cp one: The bifunctional complex 1 facilitates the interaction with substrates bearing less electrophilic carbon atoms than ketones, epoxides, and imides. The title reaction was applicable to the reduction of Evans' asymmetric alkylation products to the chiral alcohols along with good recovery of the chiral oxazolidinone auxiliary. EWG = electron-withdrawing group.
