The hydroformylation of 10‐undecenenitrile (1) – a substrate readily prepared from renewable castor oil – in the presence of rhodium‐phosphane catalysts systems is reported. The corresponding linear aldehyde (2) can be prepared in high yields and regioselectivities with a (dicarbonyl)rhodium acetoacetonate‐biphephos [Rh(acac)(CO)2‐biphephos] catalyst. The hydroformylation process is accompanied by isomerization of 1 into internal isomers of undecenenitrile (1‐int); yet, it is shown that the Rh‐biphephos catalyst effectively isomerizes back 1‐int into 1, eventually allowing high conversions of 1/1‐int into 2. Recycling of the catalyst by vacuum distillation under a controlled atmosphere was demonstrated over 4–5 runs, leading to high productivities up to 230,000 mol (2)⋅mol (Rh)−1 and 5,750 mol (2)⋅mol (biphephos)−1. Attempted recycling of the catalyst using a thermomorphic multicomponent solvent (TMS) phase‐separation procedure proved ineffective because the final product 2 and the Rh‐biphephos catalyst were always found in the same polar phase. Auto‐oxidation of the linear aldehyde 2 into the fatty 10‐cyano‐2‐methyldecanoic acid (5) proceeds readily upon exposure to air at room temperature, opening a new effective entry toward polyamide‐12.magnified image

Linear α-olefins (LAO) are one of the main targets in the field of surfactants, lubricants, and polymers. With the depletion of petroleum resources, the production of LAO from renewable feedstocks has gained increasing interest in recent years. In the present study, we demonstrated that Ir catalysts were suitable to decarbonylate a wide range of biosourced substrates under rather mild conditions (160 °C, 5 h reaction time) in the presence of potassium iodide and acetic anhydride. The resulting LAO were obtained with good conversion and selectivity provided that the purity of the substrate, the nature of the ligand, and the amounts of the additives were controlled accurately. The catalytic system could be recovered efficiently by using a Kugelrohr distillation apparatus and recycled.