829-85-6Relevant articles and documents
Reaction of secondary phosphine chalcogenides with diallylamine
Verkhoturova,Kazantseva,Arbuzova,Albanov,Gusarova,Trofimov
, (2014)
Diphenyl- or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl phosphine chalcogenides. The yield and the ratio of
Indium(III) promoted oxidative P-P coupling of silylphosphines
Cartlidge, Ashleigh J.,Matthews, Peter D.
, (2022/01/28)
The reaction of indium(III) salts with Ph2PSiMe3 and PhP(SiMe3)2 gives rise to a one- and two-electron reductive P-P coupling respectively, with the formation of new P-P bonds resulting in the preparation of (Ph2P)2 and the cyclicoligophosphane compounds (PhP)4 and (PhP)6.
Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
Cammarata, Jose,Gschwind, Ruth M.,Lennert, Ulrich,Rothfelder, Robin,Scott, Daniel J.,Streitferdt, Verena,Wolf, Robert,Zeitler, Kirsten
supporting information, p. 24650 - 24658 (2021/10/14)
Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
Phosphirenium ions as masked phosphenium Catalysts: Mechanistic evaluation and application in synthesis
Gasperini, Danila,Neale, Samuel E.,Mahon, Mary F.,MacGregor, Stuart A.,Webster, Ruth L.
, p. 5452 - 5462 (2021/06/01)
The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Ha'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.