Autotandem Catalysis with Ruthenium: Remote Hydroesterification of Allylic Amides

A one-pot tandem sequence involving olefin isomerization and hydroesterification has been developed that enables the incorporation of a C-1-unit at the remote terminal position of allylic amides. Key observations suggest that generation of an active ruthenium hydride, formed by addition of acetic acid, allows both processes to take place under mild conditions in an autotandem catalytic, cascading fashion, which is characterized by the use of a single catalytic entity capable of promoting multiple distinct steps without operator intervention.