Properties and Catalytic Activities of New Easily‐Made Amphiphilic Phosphanes for Aqueous Organometallic Catalysis

Abstract

Mono-and disulfonated amphiphilic versions of triphenylphosphane (PPh 3 ) and cyclohexyl-A C H T U N G T R E N N U N G (phenyl)phosphane were easily synthesized from commercial reagents and sulfuric acid. The behaviour of these phosphanes in solution was investigated by surface tension, isothermal titration calorimetry, nuclear magnetic resonance and cryo-transmission electron microscopy. Two different supramolecular assemblies were evidenced according to the degree of sulfonation. The monosulfonated phosphanes formed well organized micelle-like aggregates while the disulfonated phosphanes formed heterogeneous and disorganized vesicle-like assemblies. The efficiency of these amphiphilic phosphanes was evaluated in the aqueous biphasic, palladium-catalyzed cleavage of allyl alkyl carbonates.

Cyclodextrin/Amphiphilic Phosphane Mixed Systems and their Applications in Aqueous Organometallic Catalysis

“…The recently described phosphane 1 (Figure 1)21 has been used as both micelle‐constitutive building block and water soluble rhodium‐stabilizing ligand. In the studied catalytic system, phosphane 1 was always used in excess regarding the rhodium precursor (5 equiv.).…”

Homogenous catalytic hydrogenation of bicarbonate with water soluble aryl phosphine ligands

“…The sulfonated biaryl monophosphine [20,21] and aryl diphosphine [22][23][24] ligands were synthesized according to literature procedures. All other chemicals are commercial products and were used as received.…”

“…Furthermore, small 1 J P-Se coupling constants indicate stronger basicity of the ligand and that the P center is more electron donating. In their studies, Ferreira et al [21] reported that the presence of an additional phenyl group counterbalanced the electron-withdrawing and deactivating effect of the sulfonate group, as indicated by the respective 1 J P-Se values ( Table 1). Indeed ligands MBMS (L1), Ph(P(bisbiph)DS (L3) and P(biph) 3 TS (L4) are assumed to have equal basicities ( 1 J P-Se 739 Hz).…”

In Situ Dearomatisation/Alkylation of Arylphosphane Derivatives

“…This means that any preparation of a modified phosphane by an analogous pathway is likely to be tedious, because the synthesis usually has to be reproduced in its totality. [8] Directed ortho-metallation reactions, very popular methods for the functionalisation of arenes in classical organic chemistry, [9] have to date found little use in organophosphorus chemistry. Such an approach, which treats phosphanes as the starting point in the synthetic pathway, can obviously provide a step-economical synthesis of new compounds through a wide range of transformations.…”