6224-63-1Relevant articles and documents
Photochemical transformation of chlorobenzenes and white phosphorus into arylphosphines and phosphonium salts
Gschwind, Ruth M.,Mende, Michael,Scott, Daniel J.,Streitferdt, Verena,Till, Marion,Wolf, Robert
supporting information, p. 1100 - 1103 (2022/02/03)
Chlorobenzenes are important starting materials for the preparation of commercially valuable triarylphosphines and tetraarylphosphonium salts, but their use for the direct arylation of elemental phosphorus has been elusive. Here we describe a simple photochemical route toward such products. UV-LED irradiation (365 nm) of chlorobenzenes, white phosphorus (P4) and the organic superphotoreductant tetrakis(dimethylamino)ethylene (TDAE) affords the desired arylphosphorus compounds in a single reaction step.
A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
supporting information, (2022/01/04)
The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
Superbase-Assisted Selective Synthesis of Triarylphosphines from Aryl Halides and Red Phosphorus: Three Consecutive Different SNAr Reactions in One Pot
Malysheva, Svetlana F.,Kuimov, Vladimir A.,Belogorlova, Natalia A.,Albanov, Alexander I.,Gusarova, Nina K.,Trofimov, Boris A.
supporting information, p. 6240 - 6245 (2019/11/05)
Aryl halides, ArX (Ar = Ph, 2-, 3- and 4-Tol, 1- and 2-Np, 4-C6H4CONH2; X = F, Cl, Br), rapidly and exothermically (100–180 °C, 0.5–2 h) react with red phosphorus in superbase systems KOH/L, where L is a polar nonhydroxylic complexing solvent (ligand), such as NMP, DMSO, HMPA, to afford the corresponding triarylphosphines (Ar3P) in up to 74 % yield (for X = F). Thus, three consecutive reactions of SNAr (aromatic nucleophilic substitution) to form the three C(sp2)–P bonds are realized in one pot. The synthesis is mostly chemoselective (with rare exception): neither mono- nor diphosphines have been isolated. The best results were attained when aryl fluorides were treated with red phosphorus (Pn) in the KOH/NMP superbase system. This environmentally friendly, PCl3-free synthesis of Ar3P from available starting materials opens an easy and straightforward access to triarylphosphines, which are important ligands, synthetic auxiliaries, and components of high-tech- and medicinally oriented complexes.
