13639-74-2Relevant articles and documents
Labile P-C bonds: P-(phosphinoyl)methyl-λ5-phosphazenes and related compounds
Alajarín, Mateo,López-Leonardo, Carmen,Llamas-Lorente, Pilar
, p. 1041 - 1043 (2001)
N-Aryl-P,P-diphenyl-P-(diphenylphosphinoyl)methyl-λ5-pho sphazenes undergo smooth acid-catalysed hydrolysis with concomitant P-C bond fission yielding N-aryl-P,P-diphenylphosphinamides and diphenylmethylphosphane oxide. A tentative mechanistic explanation is given.
Indolizy Carbene Ligand. Evaluation of Electronic Properties and Applications in Asymmetric Gold(I) Catalysis
Fensterbank, Louis,Forté, Jérémy,Gontard, Geoffrey,Lemière, Gilles,Martinez, Thibaut,Mouriès-Mansuy, Virginie,Troufflard, Claire,Vanitcha, Avassaya,Vanthuyne, Nicolas
supporting information, p. 19879 - 19888 (2021/08/06)
We report herein a new family of carbene ligands based on an indolizine-ylidene (Indolizy) moiety. The corresponding gold(I) complexes are easily obtained from the gold(I)-promoted cyclization of allenylpyridine precursors. Evaluation of the electronic pr
Intramolecular nucleophilic substitution of ω-haloalkylphosphine derivatives
Pawe?, Wo?nicki,Korzeniowska, Ewelina,Stankevic, Marek
, p. 10271 - 10296 (2018/02/27)
ω-Haloalkylphosphine derivatives undergo the intramolecular nucleophilic substitution reaction upon treatment with a strong base, yielding either cycloalkylphosphine derivatives or heterocyclic phosphine derivatives. The selectivity of the cyclization of
Mixed (P=S/P=O)-stabilized geminal dianion: Facile diastereoselective intramolecular C-H activations by a related ruthenium-carbene complex
Heuclin, Hadrien,Le Goff, Xavier F.,Mezailles, Nicolas
, p. 16136 - 16144 (2013/02/23)
A new unsymmetrical geminal dianion that contained both a phosphine oxide moiety and a phosphine sulfide moiety has been synthesized. Its reactivity towards RuII was explored, which led to the formation of a highly reactive carbene complex that evolved at room temperature to yield a kinetic orthometalated RuII complex through C-H activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second C-H insertion occurred at a phenyl group of the phosphine sulfide moiety to form the thermodynamic orthometalated Ru II complex in a diastereospecific manner. DFT calculations fully rationalized the experimental findings in terms of the relative energies of the kinetic and thermodynamic products and allowed the mechanism of this process to be fully understood.
Phosphine- and thiophosphorane-amine ligands: Lithiation and coordination to Rh(I)
Payet, Elina,Auffrant, Audrey,Le Goff, Xavier F.,Floch, Pascal Le
experimental part, p. 1499 - 1506 (2010/08/03)
A series of phosphine-amine and thiophosphorane-amine ligands (PR2(X)CH2NHR′, X = lone pair, S, R = Ph, Cy, R′ = tBu, Ph) differing by the nature of the phosphorus and nitrogen substituents were synthesized. Their lithiation, in order to generate the corresponding amido ligand mainly led to dissociation with formation of phosphide or thiophosphinite anion and imine. DFT calculations confirmed that this pathway is in most cases thermodynamically favoured. But for a phosphine-amido anion featuring alkyl substituents on the P atom and phenyl on the nitrogen, calculations showed that the dissociation is strongly disfavoured (ΔG = +24.3 kcal mol-1). Actually, {PCy2CH2NPhLi} was isolated in high yield and fully characterized. This phosphine-amido ligand and the corresponding amine derivative were then coordinated to Rh(I) metal centre.
The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes
Clarke, Celia,Fox, David J.,Pedersen, Daniel Sejer,Warren, Stuart
supporting information; experimental part, p. 1329 - 1336 (2009/12/04)
Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides.
Highly atom-economic one-pot formation of three different C-P bonds: General synthesis of acyclic tertiary phosphine sulfides
Baccolini, Graziano,Boga, Carla,Mazzacurati, Marzia
, p. 4774 - 4777 (2007/10/03)
The reaction of benzothiadiphosphole 1 with an equimolar mixture of R 1MgBr and R2MgBr gave intermediate A′, which, after only 4-5 min, was treated with an equimolar amount of R3MgBr, giving the asymmetric phosphine PR1R2R3 in 45% overall yield (75-80% yield when R1 = R2 and 85-90% yield when R1 = R2 = R3) and the byproduct 6 in 90% yield. The treatment of 6 with PCl3 quantitatively regenerates the starting reagent 1. Treatment of the phosphines with elemental sulfur gave the corresponding sulfides.
Reactivity of X3P compounds with elemental sulfur, carbon disulfide or both, to yield X3PS, X3RCS2 or X3P.Sn.CS2 adducts
Demarcq, Michel C.
, p. 307 - 320 (2007/10/03)
Kinetic constants k2 have been obtained for the reaction of sulfur with 25 PIII compounds in toluene or hexane. In the series PhnMe3-nP (n = 1-3) or PhnBu3-nP (n = 0-3), log k2 decreases linearly with Σχi (χi=Tolman's electronic parameter of each ligand on P), taken as a gauge for the donor strength of P. Dramatic deviations from additivity are observed for the series PhnP(OEt)3-n, PhnP(OEt)3-n, and BunP(OEt)3-n(n = 0-3); the deviation is smaller for PhnPCl3-n, and even smaller for PhnP(NEt2)3-n . The results are discussed in terms of P-coordination (PIV vs. PV), stability and geometry of the intermediate X3P.S8 or of the transition state leading to this adduct, emphasis being laid on the donor/acceptor character of the P site. A similar dependence on X governs the reactivity of X3P with S8, CS2 or both, to give X3PS, X3P.CS2 (binary red adduct) or X3P.Sn.CS2 (ternary yellow adduct) respectively; an explanation for this parallelism is proposed.
An Unusual Property of Benzyl Diphenylphosphinothiite in the Reactions with Various Electrophilic Reagents
Drozdova, Yana A.,Burilov, Alexander R.,Pudovik, Michael A.,Gainullin, Rafinad M.,Il'yasov, Akhat V.
, p. 506 - 509 (2007/10/02)
Reactions of benzyl diphenylphosphinothiite with a number of electrophiles have been investigated. It has been proved that a kinetically controlled process affords the S-attacked product, which is further converted into the transalkylated product, whereas
