An Atom-Economical and Stereoselective Domino Synthesis of Functionalised Dienes

Open sesame: A direct synthesis of functionalised and stereodefined dienes, relying on a domino allylic alkylation/electrocyclic ring‐opening sequence, is reported. This method allows concise access to doubly vinylogous esters. A further systematic study of ring‐opening rates of carbon‐substituted cyclobutenes allowed the design of substrates amenable to sequential pericyclic reactions (see scheme).