Selective Isomerization-Hydroformylation Sequence: A Strategy to Valuable a-Methyl-Branched Aldehydes from Terminal Olefins

For the first time, an original selective isomerization-hydroformylation sequence to convert terminal olefins bearing an anionic moiety to a-methyl-branched aldehydes with unprecedented selectivities is reported. This opens up new synthetic avenues to these valuable building blocks from inexpensive and bioavailable substrates. The catalytic system involves a suitable selective monoisomerization catalyst and a selective supramolecular catalyst that preorganizes a substrate molecule prior to the hydroformylation reaction via hydrogen bonding. In principle, the strategy can be extended to other classes of substrates, providing suitable catalysts for the hydroformylation of internal alkenes.