98061-19-9

Upstream product

• 5029-67-4 2-iodopyridine 
• 93-58-3 benzoic acid methyl ester 
• 67-56-1 methanol 
• 110-86-1 pyridine 
• 610-97-9 o-iodo-methyl-benzoic acid 
• 109-04-6 2-bromo-pyridine 
• 201230-82-2 carbon monoxide 
• 485385-79-3 2-[2-(trifluoromethylsulfonyl)phenyl]pyridine 
• 133772-18-6 methyl 2-(iodomethyl)benzoate 
• 2406-65-7 n-butyltin hydride 
• 14221-01-3 tetrakis(triphenylphosphine) palladium⁽⁰⁾ 
• 1008-89-5 2-phenylpyridine 
• 124-38-9 carbon dioxide 
• 6063-88-3 methoxydimethylaluminium 

Downstream Products

• 138572-28-8 Toluene-4-sulfonate1-amino-2-(2-methoxycarbonyl-phenyl)-pyridinium; 
• 10273-89-9 2-(2-methylphenyl)pyridine 
• 98061-37-1 1-(2-(pyridin-2-yl)phenyl)methanol 

Relevant academic research and scientific papers

Palladium-Catalyzed Oxidative C–H Alkoxycarbonylation of Arenes with Alkylcarbazates Directed by N-Heterocyclic Substituents

With alkyl carbazates as the green ester source, a novel palladium-catalyzed oxidative free radical carbonylative transformation of the C–H bond on aromatic rings to produce esters has been developed. Good yields of the corresponding products have been obtained with wide functional group tolerance and excellent regioselectivity. A variety of alkyl carbazates are found to be suitable reactants for the ortho-alkoxycarbonylation on the aromatic ring.

Transition-Metal-Free Decarboxylative Arylation of 2-Picolinic Acids with Arenes under Air Conditions

A facile, transition-metal-free, and direct decarboxylative arylation of 2-picolinic acids with simple arenes is described. The oxidative decarboxylative arylation of 2-picolinic acids with arenes proceeds readily via N-chloro carbene intermediates to afford 2-arylpyridines in satisfactory to good yields under transition-metal-free conditions. This new type of decarboxylative arylation is operationally simple and scalable and exhibits high functional-group tolerance. Various synthetically useful functional groups, such as halogen atoms, methoxycarbonyl, and nitro, remain intact during the decarboxylative arylation of 2-picolinic acids.

Palladium-Catalyzed Oxidative Carbonylation of Aromatic C?H Bonds with Alcohols using Molybdenum Hexacarbonyl as the Carbon Monoxide Source

With molybdenum hexacarbonyl as the carbon monoxide source, a general palladium-catalyzed carbonylative transformation of the C?H bond on aromatic rings to produce esters has been developed. Good yields of the corresponding products have been obtained with wide functional group tolerance and excellent regioselectivity. A variety of aliphatic alcohols are suitable reactants here. (Figure presented.).

Palladium-catalyzed direct alkoxycarbonylation of aromatic C-H bonds via selective C-C cleavage of a-keto esters

A novel palladium-catalyzed direct alkoxycarbonylation of 2-arylpyridines, 2-arylquinolines, benzo[h]quinolines, 2-phenylpyrimidines, N-pyrimidine pyrroles and N-pyrimidine indoles via aromatic C-H bond activation and selective C-C cleavage of a-keto esters has been developed. The method has the advantages of wide functional group tolerance, high selectivity, broad range of substrates and good yields.

New reactivity of oxaziridine: Pd(II)-catalyzed aromatic C-H ethoxycarbonylation via C-C bond cleavage

A novel Pd(II)-catalyzed aromatic C-H ethoxycarbonylation with oxaziridine involving C-C bond cleavage is described. Various aromatic 2-phenylpyridines and related compounds as well as aryl ureas can be effectively ethoxycarbonylated. A catalytic cycle in

Rhodium(I)-catalyzed direct carboxylation of arenes with CO2 via chelation-assisted C-H bond activation

Rh-catalyzed direct carboxylation of unactivated aryl C-H bond under atmospheric pressure of carbon dioxide was realized via chelation-assisted C-H activation for the first time. Variously substituted and functionalized 2-arylpyridines and 1-arylpyrazoles underwent the carboxylation in the presence of the rhodium catalyst and a stoichiometric methylating reagent, AlMe 2(OMe), to give carboxylated products in good yields. The catalysis is proposed to consist of methylrhodium(I) species as the key intermediate, which undergoes C-H activation to afford rhodium(III), followed by reductive elimination of methane to give nucleophilic arylrhodium(I). This approach demonstrates promising application of C-H bond activation strategy in the field of carbon dioxide fixation.

Deprotonative metalation of functionalized aromatics using mixed lithium-cadmium, lithium-indium, and lithium-zinc species

In situ mixtures of CdCl2TMEDA (0.5 equiv; TMEDA = N,N,N',N'-tetramethylethylenediamine) or InCl3 (0.33 equiv) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 1.5 or 1.3 equiv, respectively) were compared with the previously described mixture of ZnCl2-TMEDA (0.5 equiv) and [Li(tmp)] (1.5 equiv) for their ability to deprotonate anisole, benzothiazole, and pyrimidine. [(tmp)3CdLi] proved to be the best base when used in tetrahydrofuran at room temperature, as demonstrated by subsequent trapping with iodine. The Cd-Li base then proved suitable for the metalation of a large range of aromatics including benzenes bearing reactive functional groups (CONEt2, CO2Me, CN, COPh) or heavy halogens (Br, I), and heterocycles (from the furan, thiophene, pyrrole, oxazole, thiazole, pyridine, and diazine series). Fivemembered heterocycles benefiting from doubly activated positions were similarly dideprotonated at room temperature. The aromatic lithium cadmates thus obtained were involved in palladium-catalyzed cross-coupling reactions or simply quenched with acid chlorides.

Synthesis of functionalized 2-arylpyridines from 2-halopyridines and various aryl halides via a nickel catalysis

An efficient nickel-catalyzed method devoted to the direct formation of functionalized 2-arylpyridines is described avoiding the prior preparation of organometallic species. Various functionalized 2-arylpyridines are obtained in moderate to excellent yields by a one-step chemical procedure from corresponding halides. The NiBr2(2,2′-bipyridine) complex appears to be an extremely suitable catalyst for the activation in the presence of manganese dust of aromatic halides and pyridyl halides functionalized by reactive groups. The versatility of this original process represents a simple alternative to most known methods using organometallic reagents.

Radical dearomatization of arenes and heteroarenes

The stannane-mediated benzeneselenol-catalyzed addition of aryl iodides to a range of arenes and aromatic hetereocycles has been studied. With furan, thiophene, and several carbocyclic arenes, the addition takes place with quenching of the adduct radical by the catalytic selenol leading to moderate yields of aryl-dihydroarenes. With nitrogen heterocycles, on the other hand, it was not possible to suppress aromatization of the adduct radical and fully aromatized products were isolated. Aryl iodides bearing hydrogen bond donating groups in the ortho-position add to nitrogen heterocycles with high selectivity ortho- to the nitrogen, affording a simple one-step synthesis of potential chelating ligands. While 2-iodophenol is an excellent aryl radical source in these reactions, the homologous 1-iodo-2-naphthol fails owing to its reaction with diphenyl diselenide, which gives 1-phenylseleno-2-naphthol in high yield.

Direct synthesis of heterobiaryls by radical addition to pyridine: Expeditious synthesis of chelating ligands

The addition of aryl radicals to pyridine may be affected in moderate yield on exposure of aryl iodides to tributyltin hydride, AIBN, and diphenyl diselenide in hot pyridine. Mixtures of ortho-, meta-, and para-aryl substituted pyridines are typically obtained. When the iodide is ortho-substituted with a hydrogen bond donor, such as o-iodophenol, significantly improved selectivity for ortho-substituted pyridines, with potential as bidentate chelating ligands, is obtained.