Continuous Production of Bifunctional Platform Chemicals From Plant Oils in Water by Cyclodextrin‐Mediated Hydroformylation

Abstract Platform chemicals from renewable resources with broad applications are highly desirable, particularly for replacing fossil‐based monomers. Bifunctional aliphatic ester‐aldehydes, accessible via regioselective hydroformylation of unsaturated oleochemicals, can be converted into linear ω‐amino/ω‐hydroxy esters and dicarboxylic acids—key building blocks for biobased aliphatic polycondensates. However, their success hinges on efficient, economically viable production, with catalyst recycling being critical. We present the Rh‐catalyzed, cyclodextrin‐mediated, aqueous biphasic hydroformylation of methyl 10‐undecenoate (from castor oil) and methyl 9‐decenoate (from rapeseed oil) to produce methyl 12‐oxododecanoate and methyl 11‐oxoundecanoate, respectively, with high yields and productivity. This system allows for efficient catalyst recycling via decantation, maintaining 30 % of its native activity in aqueous biphasic conditions. Reaction conditions were optimized using a tailored experimental design, reducing nearly 200 experiments to 39 without sacrificing predictive accuracy. The optimized conditions were transferred to a continuous miniplant, achieving a low rhodium loss of 0.018 % h −1 , with excellent space‐time yields of 76.5 kg h −1  m −3 . Rhodium in the product was as low as 79 ppb, with 4.4 kg of product per mg of catalyst lost, marking a significant step in combining hydroformylation‐derived, bio‐based platform chemicals with economic industrial potential.