Hydrovinylation Reactions – Atom‐Economic Transformations with Steadily Increasing Synthetic Potential

AbstractThe intermolecular carbon–carbon bond formation between two alkenes also known as 1,2‐hydrovinylation reaction can be realised with different transition metal catalysts. The application of styrene derivatives, norbornenes and other alkenes in asymmetric catalysis with a variety of chiral ligands leads to α‐chiral alkene products in an atom‐economic transformation. Accordingly, the 1,2‐hydrovinylation is one of just a few asymmetric transformations which produce stereogenic centres in the absence of polarised functional groups. The 1,4‐hydrovinylation of terminal alkenes and 1,3‐dienes can be controlled by the electronic nature of the alkene starting material for the selective formation of linear or branched 1,4‐dienes. These adducts can be used for the synthesis of 1,3‐ as well as 1,4‐dicarbonyl derivatives upon ozonolysis of suitable intermediates. As an extension of the 1,4‐hydrovinylation reaction a cobalt‐catalysed 1,4‐hydrobutadienylation reaction is reported where two different 1,3‐dienes react selectively for the formation of 1,3,6‐trienes.