6-Diphenylphosphinopyridin-2-(1 H)-one (6-DPPon)

Abstract

(A) Room Temperature Ambient Pressure (RTAP) Hydroformylation of Terminal Alkenes Breit and co-workers have developed a hydroformylation of terminal alkenes under mild conditions: at room temperature and under ambient pressure. A bidentate donor ligand, generated in situ by selfassembly of 6-DPPon, reacted with rhodium and created a new catalyst with unique properties. Various ligands were tested in comparison to 6-DPPon and the best results (high yield and little isomerization) were obtained with 6-DPPon. High selectivity, low catalyst loading, a high level of generality, and excellent reactivity were some promising aspects of this protocol.5 It was found that terminal alkenes can be hydroformylated in aqueous media by slightly changing the reaction conditions. Breit and co-workers investigated various surfactants, and the results indicated that polyoxyethanyl-α- tocopheryl sebacate (PTS) was the best choice. Interestingly, 6-DPPon was the best ligand for this reaction. It is worth noting that in addition to the advantages described above, with the new protocol the structure of the self-assembly catalyst is stable in water as a protic solvent; an important point for self-assembled structures. (B) Tandem Rhodium-atalyzed HydroformylationHydrogenation of Alkenes In 2012, a unique tandem reaction was designed. In this reaction, a one-pot conversion of alkenes into linear alcohols is achieved using two different transformations (hydroformylation of alkenes and aldehyde hydrogenation). The first step (hydroformylation) was mediated by a rhodium complex which was generated by coordination of two 6-DPPons, and a second step was carried out with an acylguanidine ligand. High regioselectivity and simultaneous a highly chemoselective reduction were two highlights of this work. (C) Hydroformylation of Alkynes Alkynes were hydroformylated stereo- and chemoselectively using 6-DPPon as a self-assembling ligand. In this study, several derivatives of the mentioned ligand were designed and investigated. This was the first time that dialkyl- as well as diaryl-substituted alkynes furnished E-enals with excellent chemo- and stereoselectivity. A new method to furnish arbonyl and carboxylic compounds was established by Breit and co-workers. In this method, by a combination of regioselective RTAP hydroformylation with 6-DPPon and a rhodium catalyst followed by decarboxylative Knoevenagel reaction (organocatalysis), various interesting compounds were produced.9 In all of the reactions, the presence of 6-DPPon was crucial. © Georg Thieme Verlag Stuttgart, New York.