Transfer Hydration of Dinitriles to Dicarboxamides

Abstract

We present a robust method for double transfer hydration of dinitriles to afford diamides. The transfer hydration of 1,n-dinitriles (n = 1–6) proceeds smoothly in the presence of a palladium(II) catalyst with acetamide as a water donor, affording the corresponding diamides in moderate to high yields, without involving significant side reactions such as monohydration or cyclization. The equilibrium was shifted in the forward direction by removing coproduced acetonitrile under reduced pressure.

Cluster Preface: Metathesis Reactions beyond Olefins

“…8 Finally, Naka and Naraoka report on a different yet similar type of reversible reaction, a reaction which transfers a molecule of water between a primary amide and a nitrile under palladium catalysis. 9 This shuttle catalysis reaction enables the synthesis of dicarboxamides using the release of volatile acetonitrile as a driving force, providing a mild entry into selective hydrolysis of nitriles.…”