1448632-01-6

Upstream product

• 4559-70-0 Diphenylphosphine oxide 
• 247018-51-5 4-t-butylphenyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate 
• 98-54-4 para-tert-butylphenol 
• 35779-04-5 1-tert-butyl-4-iodobenzene 
• 1710-98-1 p-tert-butyl benzoyl chloride 
• 98-73-7 4-(1,1-dimethylethyl)benzoic acid 
• 791-28-6 Triphenylphosphine oxide 
• 3972-56-3 4-(tert-butyl)chlorobenzene 
• 19115-00-5 sodium salt of diphenyl phosphine oxide 
• 2959-74-2 benzyldiphenylphosphine oxide 
• 175477-25-5 p-tert-butylphenoxydiphenylphosphine 
• 3972-65-4 1-bromo-4-tert-butylbenzene 
• 43100-38-5 4-tert-butylbenzoic acid hydrazide 
• 84563-54-2 bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate 

Relevant academic research and scientific papers

Visible-light-mediated semi-heterogeneous black TiO2/nickel dual catalytic C (sp2)-P bond formation toward aryl phosphonates

The combination of black TiO2 nanoparticles (NPs) with a nickel catalyst provides a low-cost, sustainable, and reusable alternative dual catalytic system to a homogeneous counterpart (noble metals). This black TiO2-photoredox/nickel dual catalytic system has efficiently driven C-P bond formation between aryl iodides and diarylphosphine oxides under visible light, providing good to excellent yields as well as tolerating a variety of functional groups. The practical application of this semi-heterogeneous protocol has been highlighted by a sunlight experiment, a gram-scale reaction, and a reusability test.

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.

NiCl 2as a Cheap and Efficient Precatalyst for the Coupling of Aryl Fluorosulfonate and Phosphite/Phosphine Oxide

Herein, NiCl 2is employed as a cheap precatalyst in the formation of C(sp 2)-P bond via cross-coupling reaction of phenol derivatives and phosphine oxides/phosphites. This catalytic system allows a variety of phenols with diverse functional groups to transform into phosphates with good yields. No additional additive is used in this reaction.

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.

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.

Selective C-P(O) Bond Cleavage of Organophosphine Oxides by Sodium

Sodium exhibits better efficacy and selectivity than Li and K for converting Ph3P(O) to Ph2P(OM). The destiny of PhNa co-generated is disclosed. A series of alkyl halides R4X and aryl halides ArX all react with Ph2P(ONa) to produce the corresponding phosphine oxides in good to excellent yields.

Palladium-catalyzed solvent-free preparation of arylphosphonates Arp(O)(OAr)2 from (Aro)3p via the Michaelis-Arbuzov rearrangement

The Pd-catalyzed Michaelis-Arbuzov rearrangement of triaryl phosphites to produce the corresponding arylphosphonates in good to excellent yields is disclosed. In comparison to the traditional methods, this new method is highly atom efficient and is general, as it can be readily extended to aryl phosphonites and phosphinites. A gram-scale reaction of (PhO)3P to PhP(O)(OPh)2 with low loading of the catalyst was also demonstrated to show its potentially practical usefulness. A plausible mechanism is proposed.

Practical C–P bond formation via heterogeneous photoredox and nickel synergetic catalysis

An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis. This platform utilizing cadmium sulfide semiconductors as heterogeneous photocatalysts and

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.

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.