A water-soluble phosphite derived from sulfonated calix[4]arene. The remarkable stability of its rhodium complexes and two phase hydroformylation studies

Stable Fluorophosphines: Predicted and Realized Ligands for Catalysis

“…[1] However, the susceptibility of P(OAr) 3 ligands to hydrolysis has necessitated the installation of large hydrophobic groups in diphosphites such as I to provide sufficient protection of the PÀO functionality to make their commercial deployment feasible. [3] Furthermore, the lability of phosphites makes their application as ligands problematic for catalytic processes in aqueous or alcoholic media [4] and with substrates containing protic functional groups. Therefore, there is a need for robust, p-acceptor ligands as alternatives to phosphites.…”

Hydroformylation in Aqueous Biphasic Media Assisted by Molecular Receptors

“…A water-soluble phosphite derived from sulfonated calix [4]arene has been recently synthesized that proved to be active in a two-phase (water/toluene) hydroformylation of 2-methylpentenoate [92]. Under 60 bar CO/H 2 at 160 C with a Rh-catalyst, branched aldehydes are the only products of hydroformylation and one of the branched aldehydes is selectively hydrogenated to give the lactone derivative.…”

Phosphorus-containing macrocyclic compounds: synthesis and properties

“…83 The reaction of tetrasulfonatocalix [4]arene 111 in the form of the tri-n-octylammonium salt with tris(dimethylamino)phosphine followed by the treatment with gaseous dimethylamine gave product 112 containing the six-coordinate phosphorus atom. 85 Since this compound is stable in the solid state even during prolonged storage, it serves as a convenient precursor in the synthesis of water-soluble ligand 113, which is easily formed in one hour by the action of water on salt 112 (Scheme 38). Scheme 38 This process is accompanied by the elimination of a dimethylamine molecule and a change in the conformation of the macrocycle.…”

“…This complex also efficiently and selectively catalyzes the phase-transfer hydroformylation of 2-methyl pentanoate to form aldehydes having exclusively a branched structure. 85 The reaction of p-tert-butylcalix [5]arene 114 with two equivalents of tris(dimethylamino)phosphine or dichlorophenylphosphine at room temperature is suitable for the introduction of two phosphorus-containing cyclic moieties into the calixarene cage giving rise to the corresponding derivatives 115 and 116. 86 The use of one equivalent of the phosphorylating agent in this reaction results in the formation of monophosphorylated calix [5]arene 117.…”