Tertiary Amines as Ligands in a Four‐Step Tandem Reaction of Hydroformylation and Hydrogenation: An Alternative Route to Industrial Diol Monomers

• Published in: ChemCatChem Vol. 9; no. 8; pp. 1436 - 1441
• Main Authors: Fuchs, Sarah, Lichte, Dominik, Dittmar, Morten, Meier, Gregor, Strutz, Heinz, Behr, Arno, Vorholt, Andreas J.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 21.04.2017
• Subjects: amines; diols; hydroformylation; Hydrogenation; Ligands; tandem reaction
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.201601518

A highly selective synthesis of diols is presented by simple auto‐tandem catalysis to connect hydroformylation and hydrogenation reactions by a rhodium‐catalyst with tertiary amines as ligands. This system allows the hydroformylation/hydrogenation of non‐conjugated cyclic olefins to selectively provide diols under mild reaction conditions. As a model substrate, the industrially relevant dicyclopentadiene (dcpd) was chosen. With the reaction system [Rh(octanoate)2]2 and triethylamine, diols are produced in a high yields of up to 79 % with full conversion of intermediate aldehyde and no evidence of olefin hydrogenation. The scope of the reaction was evaluated and the optimised reaction conditions were successfully scaled up to a 2 L reactor. Finally, the Rh/amine catalyst complex was recycled by a simple water extraction of the diol‐product. Hopscotch: how far can you jump directly? Rh complexes with tertiary amine ligands allow for a one‐pot synthesis of diols through a tandem reaction of hydroformylation and hydrogenation. Reaction conditions were optimised and successfully scaled up.