Molybdenum-Catalyzed Regio- and Enantioselective Amination of Allylic Carbonates: Total Synthesis of (S)-Clopidogrel

The first molybdenum-catalyzed highlyregio- and enantioselectiveallylic amination of both aryl- and alkyl-substituted branched allyliccarbonates has been developed. A wide variety of amines, includingdrugs and complex bioactive molecules, underwent successful aminationwith excellent reaction outcomes (up to 96% yield, >99% ee, and>20:1b/l). The reaction could be scaled up and has been applied to thetotal synthesis of chiral drug molecule (S)-clopidogrel(Plavix).

Automated summary

The first molybdenum-catalyzed highly regio- and enantioselective allylic amination of both aryl- and alkyl-substituted branched allylic carbonates has been developed. A wide variety of amines, including drugs and complex bioactive molecules, underwent successful amination with excellent reaction outcomes (up to 96% yield, >99% ee, and >20:1 b/l). The reaction could be scaled up and has been applied to the total synthesis of chiral drug molecule (S)-clopidogrel (Plavix).