Novel rhodium catalyst for asymmetric hydroformylation of styrene: Study of electronic and steric effects of phosphorus seven-membered ring ligands

The asymmetric hydroformylation of styrene catalysed by rhodium complexes modified by monodentate phosphepine ligands has been investigated. The effects of a systematic variation of the phosphorus substituent on catalytic activity and selectivity are reported as well as the outcome of a combinatorial approach for the formation of mixed ligands complexes with several commercially available ligands. Effective catalytic systems have been devised for the reaction that provide for full conversion within 24 h and regioselectivity up to 96% in the branched aldehyde and enantioselectivities up to 48%. The use of bidentate ligands built up by binaphthyl-supported seven-membered phosphacyclic units does not allow for further improvement in the reaction outcome.