10251-55-5Relevant academic research and scientific papers
High atom-economical one-pot synthesis of secondary phosphines and their borane complexes using recycling phosphorus donor reagent
Baccolini, Graziano,Boga, Carla,Mazzacurati, Marzia,Sangirardi, Federico
, p. 1677 - 1680 (2006)
A general new method for the one-pot preparation of secondary phosphines 11 and in situ generation of their borane complexes 12 is described. This method consists of the sequential addition, at room temperature, of equivalent amounts of R1MgBr and R2MgBr to 1 equiv of the phosphorus atom donor reagent 1. Final treatment with water gives secondary phosphines R 1R2PH (or the corresponding phosphine-borane complexes if treated with BH3·THF) and the end product 6, which can be recycled.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes
Gao, Li,Han, Xue-Yu,Huang, Zhuo,Liu, Xu-Teng,Sun, Ying-Ying,Wu, Yue,Zhang, Qing-Wei
supporting information, p. 11309 - 11316 (2021/08/03)
The practical synthesis of P-stereogenic tertiary phosphines, which have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, represents a significant challenge. A regio- and enantioselective hydrophosphination using cheap a
Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes
Pearce, Kyle G.,Borys, Andryj M.,Clark, Ewan R.,Shepherd, Helena J.
, p. 11530 - 11536 (2018/09/21)
Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.
Reductive cleavage of the carbon-phosphorus bond with alkali metals. III Reactions of arylalkylphosphines
Doorn, Johannes A. van,Meijboom, Nico
, p. 170 - 177 (2007/10/02)
The reductive cleavage of phenylalkylphosphines Ph2PR, PhPR2 (R = Bu, iPr) with Na/NH3 is unselective; both phenyl and alkyl groups can be cleavaged and Birch reduction may occur.Reaction of Ph2tBuP gives a high yield of diphenylphosphide.Polar groups (CO2Na, SO3Na) at the ω position of primary alkyl groups may lead to an increase in selectivity; Birch reduction is suppressed and a functionalised secondary phosphide is obtained.From diarylbenzyl- and diarylallylphosphines, the benzyl and allyl groups are selectively removed; Ar2PH and ArRPH are formed in high yield after hydrolytic work-up unless the aryl group bears F, CF3 or (CH3)2N substituents.From the reaction mixture of Ph2PCH2Ph we have isolated 1,2-diphenylethane. 2-Methoxyphenyl and 2,6-dimethoxyphenyl groups are selectively removed from Ar2BuP, ArPhBuP and Ar2P(CH2)3PAr2, forming ArBuPH, PhBuPH and ArP(H)(CH2)3(H)PAr, respectively.A double-cleavage reaction of Ar2RP may occur in low yield. 2,6-(dimethoxyphenyl-dibutylphosphine gives dibutylphosphine in moderate yield.When compounds with a 2,6-dimethoxyphenyl moiety are allowed to react with Li/THF, removal of a methyl group leads to novel phosphinophenols.It is concluded that cleavage of alkyl groups R selectively occurs when R radical is relatively stable (tBu, PhCH2> iPr > Bu).
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.
A Simple Synthesis and Some Synthetic Applications of Substituted Phosphide and Phosphinite Anions
Tsvetkov, E. N.,Bondarenko, N. A.,Malakhova, I. G.,Kabachnik, M. I.
, p. 198 - 208 (2007/10/02)
Based on data for the acidity relationship of phosphines and phosphinous acids and water in dimethyl sulfoxide and water, a simple method is reported for the generation of phosphide and phosphinite anions by the action of concentrated aqueous alkali on primary and secondary phosphines as well as phosphinous acids in dimethyl sulfoxide or other dipolar aprotic solvents.Alkylation of the anion yields secondary and tertiary phosphines, polyphosphines, functionally substituted phosphines as well as similarly substituted phosphine oxides.Phosphinous acids have beenalkylated in various solvents in two-phase systems containing concentrated aqueous alkali and tetrabutylammonium iodide as phase transfer catalyst.
