4608-06-4

Upstream product

• 21453-88-3 (E)-1-propenyltriphenylphosphonium chloride 
• 4569-35-1 (Z)-diphenyl 1,2-propenylphosphine oxide 
• 4920-02-9 diphenyl((trimethylsilyl)methyl)phosphine oxide 
• 75-07-0 acetaldehyde 
• 756-79-6 dimethyl methane phosphonate 
• 1499-21-4 Diphenylphosphinic chloride 
• 683-08-9 Diethyl methylphosphonate 
• 513-35-9 2-methyl-but-2-ene 
• 2096-78-8 vinyldiphenylphosphine oxide 
• 829-85-6 diphenylphosphane 
• 65567-06-8 lithium diphenylphosphide 
• 4559-70-0 Diphenylphosphine oxide 
• 590-15-8 trans-2-propenyl bromide 
• 1079-66-9 chloro-diphenylphosphine 

Downstream Products

• 131480-33-6 3-diphenylphosphinyl-2,6,6-trimethylhexahydropyrrolo<1,2-b>isoxazole 
• 148003-96-7 diphenyl(2-trimethylsilylpropyl)phosphine oxide 
• 148003-78-5 2-propyl(diphenyl)phosphine oxide 
• 63103-76-4 diphenyl 2-methylpropyl phosphine oxide 
• 136492-20-1 (2-methylbut-3-en-1-yl)diphenylphosphine oxide 
• 103785-70-2 (R*,R*)-3-Diphenylphosphinoylbutan-2-ol 
• 147701-16-4 diphenyl(2-phenylpropyl)phosphine oxide 

Relevant academic research and scientific papers

Copper-Catalyzed C?P Cross-Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with in situ Halogen Exchange

An efficient protocol for concurrent tandem halogen exchange/C?P cross-coupling of cycloalkenyl bromides and secondary phosphine oxides has been developed. The catalytic system is based on cheap and air-stable copper(I) iodide as the precatalyst, commercially available N,N’-dimethylethylenediamine as the ligand, and Cs2CO3 or K2CO3 as the base. The use of sodium iodide as an additive reduces the excessive use of organic bromides to near-stoichiometric by promoting the in situ transformation to the corresponding iodides. Diarylphosphine oxides undergo cycloalkenylation with 35–99 % yields and dicyclohexylphosphine oxide with 30–53 % yields. In the case of acyclic alkenyl bromides the cross-coupling products undergo conjugate addition of diphenylphosphine oxide and satisfying yields are observed only for internal olefins. In the case of aryl bromides satisfying yields (43–72 %) are observed only for sterically unhindered arenes or arenes possessing an ortho-directing group. Cycloalkenylphosphine oxides prepared in the cross-coupling reaction undergo base-catalyzed and base-promoted conjugate addition to give bis(phosphinoyl)cycloalkanes.

Enantioselective hydrophosphinylation of 1-alkenylphosphine oxides catalyzed by chiral strong Br?nsted base

A catalytic enantioselective addition of diarylphosphine oxides to 1-alkenyl(diaryl)phosphine oxides was achieved by using a chiral ureate as a chiral strong Br?nsted base catalyst. The reaction followed by the reduction of phosphine oxide moieties provid

Ni-Catalyzed C-P Coupling of Aryl, Benzyl, or Allyl Ammonium Salts with P(O)H Compounds

A methodology that allows for the construction of C-P bonds via the nickel-catalyzed cross-coupling of organoammonium salts with appropriate phosphorus nucleophiles has been developed. Aryl-, pyridyl-, benzyl-, and allyl-ammonium triflates can be employed as the electrophiles. The employed phosphorus-based nucleophiles included diaryl/dibutyl phosphine oxide, dialkyl phosphonates, and ethyl phenylphosphinate. Functional groups OMe, CN, CF3, F, Cl, C(O)NMe2, and C(O)tBu were tolerated.

Some synthetic applications of vinylphosphane oxides

Vinylphosphane oxides have been used as Michael acceptors for the diastereoselective synthesis of anti α-functionalized-β-silylated phosphane oxides and β-stannyl-, β-phenylthio- or β-phosphanyl phosphane oxides. Although the utility of these substrates as dipolarophiles was more limited, we have obtained a mixture of 3- and 4-phosphanylpyrazoles in which the latter is the major regioisomer, by 1,3-cycloaddition with N-phenylsydnone. Moreover, vinylphosphane oxides reacted with aldehydes in the presence of LDA by a Baylis-Hillman type reaction, leading to (E)-β-hydroxyphosphane oxides, which were readily converted in allenes. It is noteworthy that the application of this methodology to silylated substrates has permitted us to synthesize an interesting and more versatile silylallene.

Regio- and stereospecific cleavage of stannyloxiranes with lithium diphenylphosphide

Unsubstituted or C-substituted stannyloxiranes reacted stereospecifically with lithium diphenylphosphide to give either β-hydroxyphosphane oxides resulting from α-opening or β-phosphanyl ketones by β-opening. Furthermore, the reactivities of distannyloxir

Regio- and stereospecific cleavage of silyl- and disilylepoxides with lithium diphenylphosphide

Unsubstituted or α- and β-C-substituted silylepoxides react stereospecifically with lithium diphenylphosphide, optionally followed by methylation, to give vinylphosphonium iodides or vinylphosphine oxides resulting from α-opening and silyl enol ethers, vi

Synthesis of substituted p-stereogenic vinylphosphine oxides by olefin cross-metathesis

(Matrix presented) Substituted vinylphosphine oxides have been prepared in good yield and exclusive (E)-olefin selectivity via olefin cross-metathesis using Grubbs and Hoveyda-type ruthenium catalysts. In addition, metathesis of chiral vinylphosphine oxid

A Regiocontrolled and Stereocontrolled Synthesis of Allylsilanes from β-Silyl Enolates

The α-lithiated diphenylphosphine oxides 3 react with methyl iodide to give the phosphine oxides 4 and 5 in a ratio 3-4:1.The corresponding reaction with aldehydes gives all four diastereomeric alcohols 7-10, which are not suitable for the synthesis of allylsilanes by a Wittig-Horner reaction.The β-dimethyl(phenyl)silyl enolates 13-15 and 25-28 react with aldehydes to give aldol products with high diastereoselectivity.The benzyl and allyl ester groups can be cleaved from these aldols to give the acids 16-18 and 29-32.The acids, in turn, can be induced to undergo dec arboxylative elimination stereospecifically either in a syn or an anti sense to give the allylsilanes 19, 20, 23, 24, 33, 34 and 39-41.A similar series of reactions can be carried out with the β-trimethylsilyl enolates 45 and 46 giving the allylsilanes 49, 50, 53 and 54.

PREPARATION OF DIPHENYLVINYLPHOSPHINE OXIDES BY THE PCP PROCESS. CHOICE OF THE LEAVING CROUP.

Carbanionic conversion of alkyl into vinylphosphonates is extended to the preparation of diphenylvinylphosphine oxides.Obtention of pure products in optimized yields is closely related to the choice of the phosphate leaving group.

ALKYLIDENEDIPHOSPHONATES ET VINYLPHOSPHONATES: UNE DEMARCHE SYNTHETIQUE SELECTIVE PAR VOIE CARBANIONIQUE

Phosphonoalkylation of acylchloro-phosphates or -phosphinates in the presence of excess lithium diisopropylamide leads to direct generation of lithiated methylenediphosphonate anions.This stable type of anion can be either protonated in acidic medium to provide tetrasubstituted methylenediphosphonate or alkylated.When aliphatic or aromatic aldehydes are added spontaneous formation of vinylphosphonates is observed.This process is a simple and convenient route to diphosphonic as well as to vinylphosphonic compounds.