Rhodium-Catalyzed Hydroformylation of 1,1-Disubstituted Allenes Employing the Self-Assembling 6-DPPon System.

A rhodium-catalyzed hydroformylation of 1,1-disubstituted allenes is reported. Using a Rh(I)/6-DPPon catalyst system, one can obtain β,γ-unsaturated aldehydes in high regio- and chemoselectivity. The Z-configured product is formed with up to >95% selectivity when unsymmetrically 1,1-disubstituted allenes are submitted to the reaction conditions. This is the first time that these interesting building blocks are accessible by hydroformylation of allenes. The utility of this methodology is demonstrated by further transformations of one of the obtained products.