Selective Synthesis of (E)- and (Z)-Allyl Nitriles via Decarboxylative Reactions of Alkynyl Carboxylic Acids with Azobis(alkylcarbonitriles).

Allyl nitriles were synthesized from the reactions of arylpropiolic acids with azobis(alkylcarbonitriles) (AIBN or ACCN). In the presence of Cu(OAc)2 as a catalyst and pyridine as the solvent, the (E)-stereoisomer was formed as the major product. This transformation shows good tolerance toward alkoxy, halogen, alcohol, amine, ester, and ketone functional groups. When the reaction was conducted with the sterically bulky amine, ethyldiisopropylamine, in the absence of a copper catalyst, the corresponding (Z)-stereoisomers were formed preferentially.