56966-27-9

Upstream product

• 124066-73-5 tris(thiophenyl-2-yl)bismuth 
• 4559-70-0 Diphenylphosphine oxide 
• 188290-36-0 thiophene 
• 3437-95-4 2-Iodothiophene 
• 1003-09-4 2-bromothiophene 
• 881-89-0 phenyl thiophene-2-carboxylate 
• 1026668-29-0 bis(2-thiophenyl)iodonium tosylate 

Relevant academic research and scientific papers

Nickel-catalyzed C–P cross-coupling of (het)aryl tosylates with secondary phosphine oxides

A novel and convenient approach to the synthesis of various tertiary phosphine oxides via nickel-catalyzed cross-coupling of (het)aromatic tosylates with secondary phosphine oxides is developed. The reaction employs cheap nickel as the catalyst, 1-(2-(di-tert-butylphosphanyl)phenyl)-4-methoxypiperidine (L3) as the ligand, and pyridine as the base. This reaction produces the corresponding (het)aromatic phosphorus compounds in good to high yields. Moreover, four new tertiary phosphine oxides are reported in this process.

Mn-Catalyzed Electrooxidative Undirected C-H/P-H Cross-Coupling between Aromatics and Diphenyl Phosphine Oxides

C-P bonds are widely found in a great many bioactive compounds and functional molecules. Transition-metal-catalyzed dehydrogenative C-H/P-H cross-coupling plays a crucial part in C-P bond formation since it requires no pretreatment of substrates. Herein, we reported a Mn-catalyzed electrochemical intermolecular dehydrogenative cross-coupling between aryl C-H and diphenyl phosphine oxides. In undivided cells, a series of phosphorylation or diphosphorylation products could be obtained separately by adjusting the proportion of substrates. A catalytic amount of inexpensive Mn(II) salt was used, and no external chemical oxidants were needed in this process. A kinetic isotope effect experiment suggested that the C-H activation was not the rate-determining step.

Palladium-catalyzed C–P bond activation of aroyl phosphine oxides without the adjacent “anchoring atom”

A novel palladium-catalyzed decarbonylation of aroyl phosphine oxides to prepare phosphine oxides from carboxylic acids is developed. Without the adjacent “anchoring atom”, the challenging C–P bond activation is achieved in high selectivity. The disclosure of this reaction provides a new example of C–P bond activation and helps to extend the understanding of the property of C–P bond.

Cu/Picolinamides-Catalyzed Coupling of (Hetero)aryl Halides with Secondary Phosphine Oxides and Phosphite?

Some 4-hydroxy-picolinic acid derived amides were revealed as more efficient ligands for Cu-catalyzed coupling of (hetero)aryl halides with secondary phosphine oxides and phosphites. Only 3—5 mol% CuI and ligands were required to ensure coupling with a number of (hetero)aryl bromides and iodides to complete at 120 oC in 10—20 h.

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.

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

Nickel-Catalyzed Electrochemical Phosphorylation of Aryl Bromides

A nickel-catalyzed electrochemical cross-coupling reaction of aryl bromides with dialkyl phosphites, ethyl phenylphosphinate, and diphenylphosphine oxide has been developed. This reaction utilizes a simple undivided cell with inexpensive carbon electrodes to synthesize aryl phosphonates, aryl phosphinates, and arylphosphine oxides at room temperature. This protocol provides a mild and efficient route for the construction of C-P bond in moderate to high yields with broad substrate scope.

Decarbonylative C-P bond formation using aromatic esters and organophosphorus compounds

Ni-catalyzed C-P bond formation was achieved using aromatic esters as unconventional aryl sources. The key to success was the use of a thiophene-based diphosphine ligand (dcypt). Several aromatic esters including heteroaromatics can be coupled with phosphine oxides and phosphates, providing aryl phosphorus compounds. The synthetic utility of the method was demonstrated by application of the present protocol to the sequential coupling reactions.

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.

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.