34303-18-9

Upstream product

• 637-87-6 1-Chloro-4-iodobenzene 
• 603-35-0 triphenylphosphine 
• 734-60-1 (4-chlorophenyl)diphenylphosphane 
• 4559-70-0 Diphenylphosphine oxide 
• 1679-18-1 4-Chlorophenylboronic acid 
• 5575-51-9 tris(4-chlorophenyl)bismuthane 
• 824-72-6 P,P-dichlorophenylphosphine oxide 
• 74-11-3 para-chlorobenzoic acid 
• 122-01-0 4-chloro-benzoyl chloride 
• 1073-69-4 N-4-chlorophenylhydrazine 
• 6002-34-2 tert-butyldiphenylphosphine 
• 536-40-3 4-chlorobenzoic acid hydrazide 

Relevant academic research and scientific papers

Method for synthesizing trisubstituted arylphosphine oxide species by using diphenyl(tert-butyl)phosphine as substrate

The invention relates to a method for synthesizing a trisubstituted arylphosphine oxide species by taking diphenyl(tert-butyl)phosphine as a substrate, belonging to the technical field of organic phosphine synthesis. The method comprises the following steps: with a transition metal palladium salt as a catalyst and a hydrazine compound and diphenyl(tert-butyl)phosphine as reaction substrates, adding the reaction substrates and an alkali compound into a reaction solvent, carrying out stirring and heating, conducting reacting for a certain period of time to obtain a reaction solution, and separating and purifying the reaction solution to obtain a trisubstituted arylphosphine oxide compound, wherein the hydrazine compound is any one selected from aromatic hydrazine and aromatic heterocyclic hydrazine; and the transition metal palladium salt catalyst is selected from any one of Pd(OAc)2, Pd(dba)2 and PdCl2. Compared with a traditional synthesis method, the method has the advantages that the use of diarylphosphine oxide hydrogen is avoided, raw materials are easy to obtain, reaction conditions are mild, yield is high, and reaction selectivity is good. In general, the method is friendly to environment and simple in synthesis process, and has certain industrial application prospects.

Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds

The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.

General Oxidative Aryl C-P Bond Formation through Palladium-Catalyzed Decarbonylative Coupling of Aroylhydrazides with P(O)H Compounds

Oxidative C-C/P-H cross-coupling is achieved via Pd-catalyzed decarbonylative cross-coupling of aroylhydrazides with P(O)H compounds. The unique cooperative reaction system, especially the Br?nsted acid and bidentate phosphine ligand, allows the selective activation of the inert C-C bond and the suppression of the undesired oxidation and coordination of >P(O)-H compounds, leading to a general oxidative synthesis of aryl phosphorus compounds from easily available substrates.

Synthesis of Unsymmetrical Tertiary Phosphine Oxides via Sequential Substitution Reaction of Phosphonic Acid Dithioesters with Grignard Reagents

A facile synthetic method for unsymmetrical tertiary phosphine oxides is reported. Sequential treatment of phosphonodithioic acid S,S-di(p-tolyl) esters with two Grignard reagents enabled the stepwise introduction of different carbon substituents on the phosphorus atom. The chemical stability of dithioesters and monosubstituted thioesters has enhanced the utility of this method, rendering a wide range of organophosphorus compounds easily available.

Room Temperature C-P Bond Formation Enabled by Merging Nickel Catalysis and Visible-Light-Induced Photoredox Catalysis

A novel and efficient C-P bond formation reaction of diarylphosphine oxides with aryl iodides was achieved by combining nickel catalysis and visible-light-induced photoredox catalysis. This dual-catalytic reaction showed a broad substrate scope, excellent functional group tolerance, and afforded the corresponding products in good to excellent yields. Compared with the previously reported use of photoredox/nickel dual catalysis in the construction of C-C bonds, the methodology described herein was observed to be the first to allow for C-heteroatom bond formation.

Experimental and theoretical study on palladium-catalyzed c-p bond formation via direct coupling of triarylbismuths with p(o)-h compounds

A novel and highly efficient Pd-catalyzed cross-coupling of triarylbismuths with a variety of P(O)-H compounds has been developed that proceeds smoothly without exclusion of moisture or air and provides a general and powerful tool for the preparation of various valuable arylphosphonates, arylphosphinates, and arylphosphine oxides, with high atom-economy, operational simplicity of the procedure, and good to high yield. The coupling reaction is the first example of transition-metal-catalyzed C-P bond construction using triarylbismuth compounds as substrates. DFT calculations reveal that C-P bond formation is the rate-determing step.

Palladium-catalyzed air-based oxidative coupling of arylboronic acids with H-phosphine oxides leading to aryl phosphine oxides

We present a novel and highly efficient methodology that allows for the construction of C-P bonds via the palladium-catalyzed air-based oxidative coupling of various commercially available arylboronic acids with easily oxidized H-phosphine oxides leading to valuable aryl phosphine oxides, particularly triarylphosphine oxides, with the use of air as the green oxidant, broad substrate applicability and good to excellent yields. The described catalytic system should be an efficient complement to the Chan-Lam type reaction and be useful in synthetic programs. This journal is the Partner Organisations 2014.

Copper-catalyzed P-arylation via direct coupling of diaryliodonium salts with phosphorus nucleophiles at room temperature

A new method for copper-catalyzed P-C bond formation through reaction of phosphorus nucleophiles with diaryliodonium salts at room temperature is described. Most target products are obtained with this method in high yields within a short reaction time of 10 min. It can be easily adapted to large-scale preparations. When unsymmetrical iodonium salts are employed, nucleophilic substitution occurs preferentially on the sterically hindered aromatic ring or the more electron-deficient ring.

Nickel-catalyzed C-P cross-coupling of arylboronic acids with P(O)H compounds

A novel and efficient Ni-catalyzed coupling of a wide range of arylboronic acids with H-phosphites, H-phosphinate esters, and H-phosphine oxides has been developed, providing a general and powerful tool for the synthesis of various aryl-phosphorus compounds, especially for valuable triarylphosphine oxides, in good to excellent yield. This protocol is the first Ni-catalyzed C-P bond-forming reaction between arylboronic acids and P(O)H compounds.

Homolytic substitution at phosphorus for the synthesis of alkyl and aryl phosphanes

(Chemical Equation Presented) A transition-metal-free radical phosphonation using Me3SnPPh2 and the less toxic Me 3SiPPh2 is reported. These readily available reagents react highly efficiently with primary and secondary alkyl radicals. Moreover, aryl radicals and tertiary alkyl radicals are phosphonated with Me 3SnPPh2 (see scheme; R = aryl, alkyl, vinyl; X = 1, Br, OC(S)imidazolyl). DFT calculations provide insights into the mechanism of the reaction.