Hydroformylation is an excellent atom-economical, catalytic one-carbon homologation reaction, in which a rhodium or cobalt catalyst is used in the presence of syngas (1:1 CO/H2) to achieve synthesis of aldehydes. In addition, hydroformylation is the largest industrial process for the synthesis of commodity chemicals (18 billion pounds per year). The hydroformylation of allenes is notably more challenging than hydroformylation of alkanes, due to undesired side reactions that contributes to the dearth of this chemistry in the literature. On a brighter note, the hydroformylation of allenes is synthetically very useful because it provides functional group handles for a diverse range of chemical transformations, and therefore presents a rapid, atom-economical route to value-added compounds. Remarkably, current results suggest that efficient hydroformylation of 1,1,3-trisubstituted allenes can be achieved using a Rh catalyst supported by a BisDiazaPhos (BDP) ligand. The ligand identity is key to achieving high regioselectivity, while the mild reaction conditions minimize competing isomerization and hydrogenation to produce β,δ-unsaturated aldehydes and their derivatives in excellent yields.

Efficient hydroformylation of 1,1,3-trisubstituted allenes

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.