Substrates containing potentially sensitive functional groups like enolizable ketones (7), alkyl chlorides (8), terminal (9) or trisubstituted alkenes (10), or aryl groups (11) were isomerized to the target products in ~90% yield. Di-and trisubstituted ketones (12, 13) and lactone 14 underwent isomerization in good to moderate yield. Reactions with functionalized arylalkenes proceeded with moderate yields (16-18), as did itaconic acid derivative 19. Notably, the majority of enal or arylalkene substrates gave poor conversions and yields when using RhCl3based conditions, suggesting the general benefit of an HAT approach in comparison to a metalhydride based reactivity.