6840-27-3

Upstream product

• 3955-72-4 3-methylphenyl tosylate 
• 4559-70-0 Diphenylphosphine oxide 
• 108-39-4 3-methyl-phenol 
• 625-95-6 3-Iodotoluene 
• 791-28-6 Triphenylphosphine oxide 
• 32578-31-7 3-tolyl triflate 
• 13050-47-0 3-methylbenzoyl hydrazine 
• 1079-66-9 chloro-diphenylphosphine 
• 108-41-8 1-chloro-3-methylbenzene 
• 644-97-3 Dichlorophenylphosphine 
• 172487-18-2 ethyl Phenylphosphinate 
• 591-17-3 meta-bromotoluene 
• 262373-15-9 4-methyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 620-22-4 3-Methylbenzonitrile 

Relevant academic research and scientific papers

Palladium anchored on a covalent organic framework as a heterogeneous catalyst for phosphorylation of aryl bromides

A simple azine-linked covalent organic framework (COF) with high thermal and chemical stabilities has been prepared by using deep eutectic solvent (DES) as green media. The as-synthesized COF was employed as heterogeneous ligand for immobilization of PdII. The obtained Pd-supported COF nanoparticles catalyst (defined as Pd/TFPT-Azine-COF) was found to be an efficient heterogeneous catalyst for the Hirao reaction of aryl halides and dialkyl phosphites or diphenylphosphine oxide with excellent recyclability, reusability, and retention of crystallinity.

Visible-Light Driven C-P Bond Formation with Recyclable Carbon Nitride Photocatalyst

The development of metal-free chemical process with recyclable heterogeneous catalyst under ambient conditions is highly desired in industrial production, especially for pharmaceutical purpose. We herein reported the efficient synthesis of pharmaceuticall

Visible-light-induced ligand to metal charge transfer excitation enabled phosphorylation of aryl halides

We herein described a visible light induced nickel(II)-catalyzed cross-coupling of secondary phosphine oxides with aryl halides. The Ni(I)species and chlorine atom radical Cl˙ were generatedviathe ligand to metal charge transfer (LMCT) process of the NiCl2(PPh3)2, which allows nickel(IV)-phosphorus speciesin situformation, giving various tertiary phosphine oxides under photocatalyst-free conditions.

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.

Microwave assisted P–C coupling reactions without directly added P-ligands

Our group introduced a green protocol for the Pd(OAc)2- or NiCl2-catalyzed P–C coupling reaction of aryl halides and various > P(O)H-compounds under MW conditions without directly added P-ligands. The reactivity of a few aryl derivatives in the Pd(OAc)2-catalyzed Hirao reaction was also studied. An induction period was observed in the reaction of bromobenzene and diphenylphosphine oxide. Finally, the less known copper(I)-promoted P–C coupling reactions were investigated experimentally. The mechanism was explored by quantum chemical calculations.

Palladium-Catalyzed C-P Bond-Forming Reactions of Aryl Nonaflates Accelerated by Iodide

An iodide-accelerated, palladium-catalyzed C-P bond-forming reaction of aryl nonaflates is described. The protocol was optimized for the synthesis of aryl phosphine oxides and was found to be tolerant of a wide range of aryl nonaflates. The general nature of this transformation was established with coupling to other P(O)H compounds for the synthesis of aryl phosphonates and an aryl phosphinate. The straightforward synthesis of stable, isolable aryl nonaflates, in combination with the rapid C-P bond-forming reaction allows facile preparation of aryl phosphorus target compounds from readily available phenol starting materials. The synthetic utility of this general strategy was demonstrated with the efficient preparation of an organic light-emitting diode (OLED) material and a phosphonophenylalanine mimic.

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.

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.

Copper-Catalyzed Addition of H-P(O) Bonds to Arynes

An efficient P-arylation of secondary phosphine oxides has been achieved through the ligand-free copper-catalyzed addition of H-P(O) bonds to in situ generated arynes at room temperature. This transformation provides a straightforward route to the formation of the aryl-P bond with wide functional group compatibility, which produces arylphosphine oxides in up to 99% yield.