An Organocatalytic Cope Rearrangement

The first example of an organocatalytic Cope rearrangement is reported. Acyclic and cyclic acyl hydrazides catalyze the rearrangement of 1,5‐hexadiene‐2‐carboxaldehydes via iminium ion formation. A correlation between ring size and catalyst activity was observed for the cyclic hydrazides, with seven‐ and eight‐membered‐ring catalysts being the most active. Diazepane carboxylate 5 c (10 mol %) catalyzed the rearrangement of a range of dienes at room temperature in acetonitrile using triflic acid as a co‐catalyst. Preliminary proof of principle for asymmetric catalysis was provided by rearrangement of 3,3‐dimethyl‐7‐phenyl‐1,5‐heptadiene‐2‐carboxaldehyde in the presence of a novel 7‐substituted diazepane carboxylate.