Intramolecular hydroformylation of allyldiphenylphosphine using a monodentate phosphorus diamide based rhodium catalyst: An NMR study

Article abstract of DOI:10.1021/om000890r

The stepwise intramolecular hydroformylation reaction of allyldiphenylphosphine using a monodentate phosphorus diamide based rhodium catalyst has been studied using NMR spectroscopy. Reaction of the rhodium-hydride complex HRhL₃CO (L = triethylbiuretphenylphosphorus diamide) with allyldiphenylphosphine results in the formation of HRhL₂-(allylPPh₂)CO. This compound undergoes hydride migration to form a cyclic rhodium-alkyl complex. When carbon monoxide is added to this complex, ligand exchange and CO insertion occur, leading to the formation of the cyclic rhodium-acyl complex Rh(CO)CH₂CH₂ CH₂PPh₂L(CO)₂. Addition of hydrogen completes the cycle forming the coordinated hydroformylated allyldiphenylphosphine ligand. The aldehyde-functionalized phosphine ligand is hydrogenated to the corresponding alcohol.