20013-55-2

Upstream product

• 696-62-8 para-iodoanisole 
• 577-19-5 2-nitrophenyl bromide 
• 609-73-4 o-nitroiodobenzene 
• 22868-26-4 (p-methoxyphenyl)dimethylsilanol 
• 5720-07-0 4-methoxyphenylboronic acid 
• 88-73-3 2-Chloronitrobenzene 
• 251453-07-3 1-chloro-1-(4'-methoxyphenyl)silacyclobutane 
• 7722-84-1 dihydrogen peroxide 
• 497-19-8 sodium carbonate 
• 33397-21-6 tris(4-methoxyphenyl)bismuth 
• 66107-29-7 4-methoxyphenyl triflate 
• 15163-59-4 potassium o-nitrobenzoate 
• 150-76-5 4-methoxy-phenol 
• 104-92-7 1-bromo-4-methoxy-benzene 

Downstream Products

• 38088-95-8 8-methoxyphenanthridine-6(5H)-one 
• 855243-98-0 4-chloro-benzoic acid-(4'-methoxy-biphenyl-2-ylamide) 
• 855622-97-8 6-(4-chloro-phenyl)-8-methoxy-phenanthridine 
• 6933-49-9 2-methoxy-9H-carbazole 

Relevant academic research and scientific papers

Tuning the ambipolar charge transport properties of tricyanovinyl-substituted carbazole-based materials

A series of push-pull carbazole-based compounds has been experimentally and theoretically characterized in combination with the X-ray analysis of the corresponding single crystals. The introduction of the strong electron-withdrawing tricyanovinyl group in the carbazole core affords electron-transporting ability in addition to the characteristic hole-transporting properties exhibited by donor carbazole derivatives.

Pd-catalyzed decarboxylative couplings of arenecarboxylic acids with aryl iodides

The combination of palladium chloride with BINAP shows high efficiency in the decarboxylative cross-coupling reactions of arenecarboxylic acids with aryl iodides. The reactions proceed smoothly to generate the corresponding biaryl compounds in good to excellent yields.

Anchored Pd(0) Nanoparticles on Synthetic Talc for the Synthesis of Biaryls and a Precursor of Angiotensin II Inhibitors

The palladium-catalyzed Suzuki-Miyaura cross-coupling reaction is one of the most important and efficient reactions to prepare a variety of organic compounds, including biaryls. Despite the overwhelming number of reports related to this topic, some methodological difficulties persist in terms of catalyst handling, recovery, and reuse, as well as the reaction media. This work reports the rational design of new, efficient, cost-effective, and reusable palladium catalysts supported on synthetic talc for the Suzuki-Miyaura reaction. From the results, key points were identified: both designed catalysts accelerated the reaction in EtOH and an open-flask setup, affording moderate to excellent yields within a short time (e.g., 30 min) even for deactivated aryl halides; the protocol can be applied to a great number of both cross-coupling partners, showing an excellent functional group tolerance; the catalysts can be recovered and reused without significant loss of activity. This protocol was used for the synthesis of a precursor of angiotensin II inhibitors such as valsartan, losartan, irbesartan, and telmisartan.

NaI/PPh3-Mediated Photochemical Reduction and Amination of Nitroarenes

A mild transition-metal- and photosensitizer-free photoredox system based on the combination of NaI and PPh3 was found to enable highly selective reduction of nitroarenes. This protocol tolerates a broad range of reducible functional groups such as halogen (Cl, Br, and even I), aldehyde, ketone, carboxyl, and cyano. Moreover, the photoredox catalysis with NaI and stoichiometric PPh3 provides also an alternative entry to Cadogan-type reductive amination when o-nitrobiarenes were used.

Visible-light-driven Cadogan reaction

Visible-light-driven photochemical Cadogan-type cyclization has been discovered. The organic D-A type photosensitizer 4CzIPN found to be an efficient mediator to transfer energy from photons to the transient intermediate that breaks the barriers of deoxygenation in Cadogan reaction and enables a mild metal-free access to carbazoles and related heterocycles. DFT calculation results indicate mildly endergonic formation of the intermediate complex of nitrobiarenes and PPh3, which corresponds with experimental findings regarding reaction temperature. The robust synthetic capacity of the photoredox Cadogan reaction systems has been demonstrated by the viable productivity of a broad range of carbazoles and related N-heterocycles with good tolerance of various functionalities.

Pd-Catalysed Suzuki-Miyaura cross-coupling of aryl chlorides at low catalyst loadings in water for the synthesis of industrially important fungicides

The Suzuki-Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis of crop protection-relevant active ingredients in water is disclosed. Optimisation of the reaction conditions allowed running the reaction with 50 ppm of Pd-catalyst loading without an additional organic solvent in the cross-coupling reaction step in short reaction times. The system was optimised for the initial cross-coupling step of the large scale produced fungicides Boscalid, Fluxapyroxad and Bixafen up to 97% yield. It is also shown that the Suzuki-Miyaura reaction can be easily scaled up to 50 g using a simple product separation and purification using environmentally benign solvents in the work-up. To show the usability of this method, it was additionally applied in the three-step synthesis of the desired active ingredients.

ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME

An organometallic compound and an organic light-emitting device including the same.

Copper catalysed Gomberg-Bachmann-Hey reactions of arenediazonium tetrafluoroborates and heteroarenediazonium o-benzenedisulfonimides. Synthetic and mechanistic aspects

Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst and gave rise to biaryls or heterobiaryls in good yields and in mild reaction conditions. A computational study of some key points of the reaction was performed. The results are coherent with the experimental data and confirm some aspects of the mechanism. The reaction free energies for the reduction in benzene by CuI of a set of 40 (hetero)arenediazonium tetrafluoroborates were calculated. Both the experiments and the calculations showed that in the coupling with substituted solvents (toluene, bromobenzene, nitrobenzene and anisole) the binding to the ortho position was always favoured.

Highly efficient palladium-catalyzed cross-coupling of diarylborinic acids with arenediazoniums for practical diaryl synthesis

A highly efficient cross-coupling of cost-effective diarylborinic acids with both isolatable and latent arenediazoniums, i.e. tetrafluoroborates and aryltriazenes, respectively, has been developed with a practical palladium catalyst system under base-free conditions in open flask at room temperature. A variety of electronically and sterically various biaryls, in particular, those bearing a coordinative ortho-substituent, could be obtained in good to excellent yields by using 0.3 mol% palladium acetate as catalyst. Features of the protocol including cost-effectiveness of diarylborinic acids, efficacy to heteroatom ortho-substituted substrates and high chemoselectivity to aryl chlorides have been clearly demonstrated in practical synthesis of fungicide Boscalid.

Tetramethylammonium fluoride tetrahydrate-mediated transition metal-free coupling of aryl iodides with unactivated arenes in air

Biaryls are important compounds with widespread applications in many fields. Tetramethylammonium fluoride tetrahydrate was found to promote the biaryl coupling of aryl iodides bearing electron-withdrawing substituents with unactivated arenes. The reaction takes place at temperatures between 100 and 150°C and can be applied to a wide range of aromatic and heteroaromatic rings, affording the products in moderate to high yields. The reaction does not require strong bases or expensive additives that are employed in the existing methods and can be conducted in air and moisture without any precautions.