Direct Synthesis of an α,ω-Diester from 2,7-Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

A new tandem catalytic process was designed and developed as a tool for the direct conversion of the widely available feedstock 2,7‐octadienol into an α,ω‐diester. This innovative auto‐tandem catalysis is atom efficient and consists of three consecutive palladium‐catalysed reactions: ether formation, ether carbonylation and alkoxycarbonylation. By using the design of experiments (DoE) approach, significant parameters were determined and the yield of the desired α,ω‐diester was optimised. Model substrates allowed deeper insight into the progress of the reaction to be gained and, as a result, the reaction sequence was uncovered. Furthermore, by simply applying other ligands, a different reaction path was followed, allowing other, new tandem catalytic sequences to be explored and enabling new compounds to be obtained. Good things come in threes: A new auto‐tandem catalytic process enables direct access to C10 α,ω‐diesters from 2,7‐octadienol by merging three different reactions in sequence: ether formation, ether carbonylation and alkoxycarbonylation. Good yields of the desired diester are obtained with a Pd/Xantphos catalyst complex. The application of other ligands leads to different reaction pathways and products.