Regioselective Construction of α,α-Disubstituted Allylic Amines by the Ruthenium-Catalyzed Allylic Amination of Tertiary Allylic Acetates.

The ruthenium-catalyzed regioselective allylic amination of tertiary allylic acetates with several types of amines has been accomplished. The reaction was effectively catalyzed by Cp*RuCl2/5,5'-dimethyl-2,2'-bipyridine or its related ruthenium catalyst systems, and α,α-disubstituted allylic amines were formed as a single regioisomer in moderate to high yields.

Kinetic Resolution of Racemic and Branched Monosubstituted Allylic Acetates by a Ruthenium-Catalyzed Regioselective Allylic Etherification.

We demonstrated the kinetic resolution of racemic and branched monosubstituted allylic acetates by a ruthenium-catalyzed regioselective allylic etherification. The reaction was effectively catalyzed by the chiral ruthenium catalyst, which was generated by [RuCl2(p-cymene)]2 and (S,S)-iPr-pybox and a catalytic amount of TFA, and both the allylic etherification product and recovered allylic acetate were obtained as an enantiomerically enriched form with up to a 103 s value.