55552-24-4Relevant articles and documents
Adaptive Behavior of a Ditopic Phosphine Ligand
Renard, Nicolas,Brenner, Eric,Matt, Dominique,Gourlaouen, Christophe
, p. 2996 - 3004 (2019)
Synthetic, structural and computational studies have been performed to investigate ligand interchange in the fluxional chelate complex [RhCl3{Ph2PACH2C(OA)OEt-κ2POA}{Ph2PBCH2C(OB)OEt-κP}], which contains two hybrid phosphine-ester ligands, one acting as P,O chelator, the other as a P-monodentate ligand. The observed ligand exchange may occur according to two pathways which both involve four elementary movements: a) oxygen dissociation with formation of a lacunary octahedral RhCl3P2 intermediate; b) migration of the Cl atom trans to PA towards the position trans to PB; c) rotations of the phosphine moieties about the Rh–P bonds, these occurring either concomitantly with the Cl displacement or in a separate step; d) coordination of an oxygen atom of the second phosphine. The two pathways thus differ by conformational changes within two distinct steps. In each pathway the rate-limiting step is the one involving a movement of the two phosphines, which generates steric frictions between the two PPh2 groups. The calculated theoretical energetic spans of both pathways (ΔG≠ ≈ 17 kcal mol–1) is close to the energy barrier obtained from a variable temperature NMR study carried out in C2D2Cl4 (ΔG≠ = 15.5 kcal mol–1). While one of the pathways leads to an isomer with a Rh-bound ethoxy O atom, the other results in the isomer having the metal coordinated to the adjacent C=O group. Exchange between the two O atoms of the coordinated ester group occurs readily (ΔGTS = 12.5 kcal mol–1).
Palladium-catalyzed C(sp3)–P(III) bond formation reaction with acylphosphines as phosphorus source
Zhang, Mengyue,Ma, Zhichao,Du, Hongguang,Wang, Zhiqian
, (2020/06/29)
Palladium-catalyzed C(sp3)–P(III) bond formation reaction for alkyl substituted phosphines preparation was developed. In this reaction, various alkyl bromides and limited alkyl chlorides reacted with acylphosphine under relative mild and easily accessible condition, and differential phosphines were afforded in good yields. This reaction made up the application of palladium catalysis in C(sp3)–P(III) bond formation, and indicated a practical application of acylphosphine as a phosphination reagent.
Photoinduced Coupling Reaction of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide with Interelement Compounds: Application to the Synthesis of Thio- or Selenophosphinates
Sato, Yuki,Kawaguchi, Shin-Ichi,Nomoto, Akihiro,Ogawa, Akiya
, p. 3558 - 3567 (2017/08/16)
Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TMDPO) is a radical initiator widely used in the field of macromolecular chemistry, but not often applied in synthetic organic chemistry. We have focused on the use of TMDPO as a phosphorus source in reactions with different E - E compounds, where E - E represents a heteroatom-heteroatom bond, under photoirradiation. Interestingly, the cross-coupling reaction between TMDPO and disulfides or diselenides successfully affords thio- or selenophosphinates and thio- or selenoesters, respectively. The synthesis of series of thio- and selenophosphinates by this photoinduced cross-coupling reaction is demonstrated.
Phosphorus-carbon bond formation catalysed by electrophilic N-heterocyclic phosphines
Burck, Sebastian,Foerster, Daniela,Gudat, Dietrich
, p. 2810 - 2812 (2008/09/19)
A P-chloro-diazaphospholene catalyses the phosphorus-carbon bond formation reaction between diphenylsilylphosphine and various alkyl chlorides. The Royal Society of Chemistry 2006.
CsOH-promoted P-alkylation: A convenient and highly efficient synthesis of tertiary phosphines
Honaker, Matthew T.,Sandefur, Benjamin J.,Hargett, James L.,McDaniel, Alicia L.,Salvatore, Ralph Nicholas
, p. 8373 - 7377 (2007/10/03)
A mild and efficient method for the synthesis of tertiary phosphines and ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves and DMF at room temperature, various secondary phosphines and alkyl bromides were examined, and the results have demonstrated that this methodology offers a general synthetic procedure to produce tertiary phosphines in moderate to high yields. Optically active tertiary phosphine synthesis is also described.
Thermal Stability of Phosphinoacetic Acids
Doorn, Johannes A. van,Meijboom, Nico
, p. 1309 - 1314 (2007/10/02)
Phosphinoacetic acids decarboxylate smoothly in toluene solution at 99 deg C and the corresponding alkylphosphine is formed in quantitative yields.Electron-withdrawing substituents at the α position of the carboxylic acid lead to a large increase in the reaction rate.In contrast, electron-withdrawing substituents at the phosphorus atom lead to a small decrease in the rate.We have concluded from the substituent effects, solvent effects, and the influence of bases and acids that both the lone pair of the phosphorus atom and the carboxylate hydrogen atom play a crucial role in the reaction.A mechanism is proposed that proceeds via an ylide.Sodium phosphinocarboxylates do not decarboxylate in an aqueous solution at 95 deg C.Instead a carbon-phosphorus bond cleavage occurs probably by an intramolecular nucleophilic substitution.
SYNTHESIS OF SOME FUNCTIONALIZED PHOSPHINOCARBOXYLIC ACIDS
van Doorn, J. A.,Meijboom, N.
, p. 211 - 222 (2007/10/02)
Various functionalized phosphinocarboxylic acids have been prepared by a number of complementary methods.Reactions of relatively electron-poor secondary phosphides with electron-rich halocarboxylates in liquid ammonia give high yields of phosphinocarboxylates.The substitution reactionmay proceed by a classical SN2 mechanism or by an SN rad mechanism.Reduction of the carboxilate can be a deleterious side reaction in the preparation of phosphinoacetic acids.Several phosphinopropionic acids are prepared by the Michael adition of diphenylphosphine to unsaturated esters.A valuable method proved to be the reaction of dichlorophosphinoacetic ester with functionalized organometallic reagents. Key words: Phosphine; carboxylic acid; ligand; functionalized; synthesis; NMR data.
ELECTROCHEMICAL SYNTHESIS OF TERTIARY PHOSPHINES FROM ORGANIC HALIDES AND CHLOROPHOSPHINES
Folest, J. C.,Nedelec, J. Y.,Perichon, J.
, p. 1885 - 1886 (2007/10/02)
The electrochemical synthesis of a wide range of tertiary mono- and diphosphines has been achieved in very simple and mild conditions, in an undivided electrolytic cell with a sacrificial anode of magnesium.
