Asymmetric Hydroformylation

Abstract

Rhodium is currently the metal of choice to achieve high enantioselectivities in the hydroformylation of a relatively wide variety of alkene substrates. The elucidation of the different steps of the catalytic cycle and the characterization of the resting state, together with the discovery of several types of ligands that are able to provide high enantioselectivities, have made the rhodium-catalyzed hydroformylation a synthetically useful tool. For years, ligands containing phosphite moieties such as diphosphites and phosphine-phosphites were considered the most successful ligands to achieve high enantioselectivities for classical substrates such as styrene and vinyl acetate. In fact, the phosphite-phosphine BINAPHOS (43) and its derivatives are still today the most successful ligands in terms of selectivity and scope. For more substituted substrates, general trends can be extracted. However, recent studies showed that these general trends can be sometimes reversed by the use of the appropriate catalyst and choice of reaction conditions, clearly showing that these trends are only indicative and that there are still many challenges to be tackled in this area.

Rh/DNA Nanoparticles, Synthesis, Characterization and Catalytic Activity in “On Water” Asymmetric Hydroformylation Reaction

“…Catalytic asymmetric hydroformylation of olefins is atom economic and one of the most efficient methods for the synthesis of optically active aldehydes from cheap raw materials (olefins and syngas) in one step under moderate reaction conditions. Chiral aldehydes represent an important feedstock in the synthesis of fine chemicals, pharmaceuticals, and agrochemical products . These optically active aldehydes can be easily converted into the corresponding alcohols, carboxylic acids, and their derivatives, amines, and imines ,.…”

Synthesis and Applications in Catalysis of Metal Complexes with Chelating Phosphinosulfonate Ligands

“…97,98 Oberhauser has examined the reactivity of rhodium complexes containing chelate 3a in the hydroformylation of 1-hexene. Modification of the ligand and the transition metal will influence the outcome of the transformations leading either to the linear (normal) aldehyde or the branched (iso) aldehyde.…”

Catalytic Asymmetric Carbonylation of Prochiral Sulfonamides via C–H Desymmetrization

“…Catalytic carbonylation is one of the most straightforward processes for oxo-synthesis, and its asymmetric versions have been a great interest of synthetic chemists . Although many studies on enantioselective carbonylation have been reported over the past decades, most of the them fall into the category of asymmetric carbonylation of alkenes under the promotion of specified chiral ligands, which was usually difficult to synthesize, and more model reactions thereby in the context of enantioselective carbonylation are highly desired. In this regard, the thriving of C–H carbonylation strategy and the tremendous success of enantioselective C–H functionalization provided a new potential protocol for enantioselective carbonylation.…”