38802-08-3

Upstream product

• 7621-16-1 (+/-)-tert-butylmethylphenylphosphine 
• 24153-79-5 benzylmethyl-t-butylphenylphosphonium bromide 
• 98933-83-6 (S_p)-[(tert-butyl)(phenyl)phosphinoyl]acetic acid 
• 172487-18-2 ethyl Phenylphosphinate 
• 677-22-5 tert-butylmagnesium chloride 
• 74-88-4 methyl iodide 
• 6057-79-0 (S)-(-)-t-butyl(phenyl)phosphine oxide 
• 538311-40-9 C₁₁H₁₇OP 
• 98976-30-8 tert-Butylphenylphosphine oxide 
• 29949-69-7 tert-butylchlorophenylphosphane 
• 644-97-3 Dichlorophenylphosphine 
• 54100-47-9 (R_p)-(+)-tert-Butylphenylphosphinothioic acid 
• 98933-81-4 (S_p)-[(tert-butyl)(phenyl)phosphinoyl]acetic acid menthyl ester 
• 591-50-4 iodobenzene 

Downstream Products

• 7621-16-1 (+/-)-tert-butylmethylphenylphosphine 
• 1380217-01-5 (3-benzylcyclohexa-1,4-dien-3-yl)-tert-butylmethylphosphane oxide 

Relevant academic research and scientific papers

Synthetic LMoO2 compounds have long been of keen interest both as structural and functional models for molybdoenzymes and in their own right as catalysts for a variety of oxygen atom-transfer (OAT) reactions. Investigations of their use as cata

Palladium/Xiao-Phos-Catalyzed Kinetic Resolution of sec-Phosphine Oxides by P-Benzylation

P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, a successful kinetic resolution of rac-se

Scalable Enantiomeric Separation of Dialkyl-Arylphosphine Oxides Based on Host–Guest Complexation with TADDOL-Derivatives, and their Recovery

Several dialkyl-arylphosphine oxides were prepared, and the enantioseparation of the corresponding racemates was elaborated with host–guest complexation using TADDOL-derivatives. The crystallization conditions were optimized and two separate crystallization methods, one in organic solvent, and the other in water, were found to yield five examples of phosphine oxides with enantiomeric excess values higher than 94 %. A gram scale resolution was performed, and both enantiomers of the methyl-phenyl-propyl-phosphine oxide were separated with (R,R)- or (S,S)-spiro-TADDOL. The intermolecular interactions responsible for the enantiomeric recognition between the chiral host and guest molecules were investigated by single-crystal X-ray diffractional structural determinations. The similarities in the structural patterns of a few diastereomeric crystals were checked by powder X-ray diffraction, as well. Organic solvent nanofiltration (OSN) was used as a scalable technique for the decomposition of the corresponding phosphine oxide–spiro-TADDOL molecular complexes, and for the recovery of the phosphine oxide enantiomers and resolving agents.

Enantiodivergent Formation of C-P Bonds: Synthesis of P-Chiral Phosphines and Methylphosphonate Oligonucleotides

Phosphorus Incorporation (PI, abbreviated Π) reagents for the modular, scalable, and stereospecific synthesis of chiral phosphines and methylphosphonate nucleotides are reported. Synthesized from trans-limonene oxide, this reagent class displays an unexpected reactivity profile and enables access to chemical space distinct from that of the Phosphorus-Sulfur Incorporation reagents previously disclosed. Here, the adaptable phosphorus(V) scaffold enables sequential addition of carbon nucleophiles to produce a variety of enantiopure C-P building blocks. Addition of three carbon nucleophiles to Π, followed by stereospecific reduction, affords useful P-chiral phosphines; introduction instead of a single methyl group reveals the first stereospecific synthesis of methylphosphonate oligonucleotide precursors. While both Π enantiomers are available, only one isomer is required - the order of nucleophile addition controls the absolute stereochemistry of the final product through a unique enantiodivergent design.

Stereoselectivity of Michael Addition of P(X)-H-Type Nucleophiles to Cyclohexen-1-ylphosphine Oxide: The Case of Base-Selective Transformation

Michael addition of phosphorus nucleophiles to the unsymmetrically substituted tert-butyl(1,4-cyclohexadien-3-yl)phosphine oxide and its derivatives has been described. The addition proceeds with the formation of the mixture of two isomeric products with good yield and diastereoselectivity. The reaction of tert-butyl(cyclohexen-1-yl)methylphosphine oxide with phosphorus nucleophiles is base sensitive and might afford two epimers which differ at one chirality center. The absolute configuration of the products has been assigned on the basis of conformational and 1H NMR analysis, and the mechanism of the reaction has been discussed. The Michael addition of phosphorus nucleophiles is postulated to proceed with or without consecutive epimerization of two α-carbanions.

Aryl group - A leaving group in arylphosphine oxides

The treatment of triphenylphosphine oxide with organometallic reagents leads to the substitution of up to three phenyl substituents with the incoming carbon nucleophile. The replacement of the phenyl/aryl group in tertiary diarylalkylphosphine oxides or even aryldialkylphosphine oxides was also observed. Naphthyl-substituted phosphine oxides undergo Michael-type addition at the naphthyl group when treated with organolithium reagent.

Synthesis and properties of tert-butylphenylmethylene(chloro)phosphorane

The synthesis and properties of tert-butylphenylmethylene(chloro)phosphorane were described. The prepared chlorophosphorane reacted with alcohols and phenol with the formation of the corresponding phosphonium salts. Its reaction with carbonyl compounds le

Room temperature, palladium-mediated P-arylation of secondary phosphine oxides

We show that a broad range of aryl iodides are efficiently coupled with secondary phosphine oxides using 1 mol % of a catalyst formed in situ from tris(dibenzylideneacetone)dipalladium and Xantphos (1). Scalemic (S)-methylphenylphosphine oxide [(S)-2e] is shown to undergo arylation without detectable stereoerosion. The application of this method to the synthesis of novel P-chiral phosphines and PCP ligands is demonstrated.

Reduction of tertiary phosphine oxides with DIBAL-H

(Chemical Equation Presented) The reduction of tertiary phosphine oxides (TPOs) and sulfides with diisobutylaluminum hydride (DIBAL-II) has been studied in detail. An extensive solvent screen has revealed that hindered aliphatic ethers, such as MTBE, are optimum for this reaction at ambient temperature. Many TPOs undergo considerable reduction at ambient temperature and then stall due to inhibition. 31P and 13C NMR studies using isotopically labeled substrates as well as competition studies have revealed that the source of this inhibition is tetraisobutyldialuminoxane (TIBAO), which builds up as the reaction proceeds. TIBAO selectively coordinates the TPO starting material, preventing further reduction. Several strategies have been found to circumvent this inhibition and obtain full conversion with this extremely inexpensive reducing agent for the first time. Practical reduction protocols for these critical targets have been developed.

Synthesis of P-stereogenic phosphorus compounds. Asymmetric oxidation of phosphines under appel conditions

Racemic phosphines are converted into enantioenriched phosphine oxides via a synthetically simple, but theoretically interesting, oxidation procedure in good enantiomeric excess (up to 80%) and excellent yields (>95%). These phosphine oxides can be oxidatively coupled to provide easy access to enantiopure DiPAMPO analogues. Particularly attractive aspects of this procedure are the operational simplicity and the low cost required to synthesize these high value compounds. Copyright