1448632-02-7

Upstream product

• 791-28-6 Triphenylphosphine oxide 
• 461-81-4 1-chloro-4-(trifluoromethoxy)benzene 
• 4559-70-0 Diphenylphosphine oxide 
• 330-12-1 4-trifluoromethoxybenzoic acid 
• 139301-27-2 4-trifluoromethoxyphenylboronic acid 
• 1448631-97-7 bis(4-(trifluoromethoxy)phenyl)iodonium tetrafluoroborate 

Relevant academic research and scientific papers

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.

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.

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

Palladium-Catalyzed Direct Decarbonylative Phosphorylation of Benzoic Acids with P(O)–H Compounds

A direct decarbonylative phosphorylation of benzoic acids catalyzed by palladium was disclosed. Under the reaction conditions, a wide range of benzoic acids coupled readily with all the three kinds of P(O)–H compounds, i.e. secondary phosphine oxides, H-phosphinates and H-phosphonates, producing the corresponding organophosphorus compounds in good to high yields. This reaction could be conducted at a gram scale and applied in the late-stage phosphorylative modification of carboxylic acids drug molecules. These results well demonstrated the potential synthetic value of this new reaction in organic synthesis.

Redox-Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C?H Di- and Trifluoromethoxylation

Applications of TEMPO. catalysis for the development of redox-neutral transformations are rare. Reported here is the first TEMPO.-catalyzed, redox-neutral C?H di- and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional-group tolerance, and can be employed for the late-stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO./TEMPO+ redox catalytic cycle. Mechanistic studies also suggest that Li2CO3 plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox-neutral TEMPO. catalysis.

DIFLUOROMETHOXYLATION AND TRIFLUOROMETHOXYLATION COMPOSITIONS AND METHODS FOR SYNTHESIZING SAME

The present invention provides a compound having the structure (I), a processing of making the compound; and a process of using the compound as a reagent for the difluoromethoxylation and trifluoromethoxylation of arenes or heteroarenes.

Redox-Active Reagents for Photocatalytic Generation of the OCF3 Radical and (Hetero)Aryl C?H Trifluoromethoxylation

The trifluoromethoxy (OCF3) radical is of great importance in organic chemistry. Yet, the catalytic and selective generation of this radical at room temperature and pressure remains a longstanding challenge. Herein, the design and development of a redox-active cationic reagent (1) that enables the formation of the OCF3 radical in a controllable, selective, and catalytic fashion under visible-light photocatalytic conditions is reported. More importantly, the reagent allows catalytic, intermolecular C?H trifluoromethoxylation of a broad array of (hetero)arenes and biorelevant compounds. Experimental and computational studies suggest single electron transfer (SET) from excited photoredox catalysts to 1 resulting in exclusive liberation of the OCF3 radical. Addition of this radical to (hetero)arenes gives trifluoromethoxylated cyclohexadienyl radicals that are oxidized and deprotonated to afford the products of trifluoromethoxylation.

Radical Trifluoromethoxylation of Arenes Triggered by a Visible-Light-Mediated N?O Bond Redox Fragmentation

A simple trifluoromethoxylation method enables non-directed functionalization of C?H bonds on a range of substrates, providing access to aryl trifluoromethyl ethers. This light-driven process is distinctly different from conventional procedures and occurs through an OCF3 radical mechanism mediated by a photoredox catalyst, which triggers an N?O bond fragmentation. The pyridinium-based trifluoromethoxylation reagent is bench-stable and provides access to synthetic diversity in lead compounds in an operationally simple manner.

Catalytic C?H Trifluoromethoxylation of Arenes and Heteroarenes

The intermolecular C?H trifluoromethoxylation of arenes remains a long-standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a novel trifluoromethoxylating reagent and redox-active catalysts for the direct (hetero)aryl C?H trifluoromethoxylation. Our approach is operationally simple, proceeds at room temperature, uses easy-to-handle reagents, requires only 0.03 mol % of redox-active catalysts, does not need specialized reaction apparatus, and tolerates a wide variety of functional groups and complex structures such as sugars and natural product derivatives. Importantly, both ground-state and photoexcited redox-active catalysts are effective. Detailed computational and experimental studies suggest a unique reaction pathway where photoexcitation of the trifluoromethoxylating reagent releases the OCF3 radical that is trapped by (hetero)arenes. The resulting cyclohexadienyl radicals are oxidized by redox-active catalysts and deprotonated to form the desired products of trifluoromethoxylation.

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.