Dual Rh−Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols

Abstract An active and selective dual catalytic system to promote domino hydroformylation–reduction reactions is described. Apart from terminal, di‐ and trisubstituted olefins, for the first time the less active internal C−C double bond of tetrasubstituted alkenes can also be utilized. As an example, 2,3‐dimethylbut‐2‐ene is converted into the corresponding n ‐alcohol with high yield (90 %) as well as regio‐ and chemoselectivity (>97 %). Key for this development is the use of a combination of Rh complexes with bulky monophosphite ligands and the Ru‐based Shvo's complex. A variety of aromatic and aliphatic alkenes can be directly used to obtain mainly linear alcohols.