4423-09-0Relevant articles and documents
Isotope Effects in the p-Tolylation of Pyridine
Nakabayashi, Takeshige,Horii, Toyokazu,Kawamura, Shunichi,Abe, Yasuo
, p. 2535 - 2536 (1981)
p-Toluoyl peroxide, p-iodotuluene, and di-p-tolyl sulfone, sulfoxide, and sulfide were photolyzed in an equimolar pyridine-pyridine-d5 mixture to give rise to isomeric p-tolylpyridines (α, β, and γ) and their deuterated compounds.Isotopic distribution ratios (YH/YD) in the isomeric products were determined to be slightly larger than unity.
Decarbonylative Pd-Catalyzed Suzuki Cross-Coupling for the Synthesis of Structurally Diverse Heterobiaryls
Blakemore, David C.,Cervantes-Reyes, Alejandro,Chinigo, Gary M.,Smith, Aaron C.,Szostak, Michal
supporting information, p. 1678 - 1683 (2022/03/14)
Heteroaromatic biaryls are core scaffolds found in a plethora of pharmaceuticals; however, their direct synthesis by the Suzuki cross-coupling is limited to heteroaromatic halide starting materials. Here, we report a direct synthesis of diverse nitrogen-containing heteroaromatic biaryls by Pd-catalyzed decarbonylative Suzuki cross-coupling of widely available heterocyclic carboxylic acids with arylboronic acids. The practical and modular nature of this cross-coupling enabled the straightforward preparation of >45 heterobiaryl products using pyridines, pyrimidines, pyrazines, and quinolines in excellent yields. We anticipate that the modular nature of this protocol will find broad application in medicinal chemistry and drug discovery research.
Organocatalytic synthesis of (Het)biaryl scaffoldsviaphotoinduced intra/intermolecular C(sp2)-H arylation by 2-pyridone derivatives
Das, Tapas Kumar,Kundu, Mrinalkanti,Mondal, Biswajit,Ghosh, Prasanjit,Das, Sajal
, p. 208 - 218 (2021/12/29)
A uniqueN,O-bidentate ligand 6-oxo-1,6-dihydro-pyridone-2-carboxylic acid dimethylamide (L1) catalyzed direct C(sp2)-H (intra/intermolecular) arylation of unactivated arenes has been developed to expedite access to (Het)biaryl scaffolds under UV-irradiation at room temperature. The protocol tolerated diverse functional groups and substitution patterns, affording the target products in moderate to excellent yields. Mechanistic investigations were also carried out to better understand the reaction pathway. Furthermore, the synthetic applicability of this unified approach has been showcasedviathe construction of biologically relevant 4-quinolone, tricyclic lactam and sultam derivatives.
Suzuki-Miyaura Cross-Coupling Reaction with Potassium Aryltrifluoroborate in Pure Water Using Recyclable Nanoparticle Catalyst
Kawase, Misa,Matsuoka, Kyosuke,Shinagawa, Tsutomu,Hamasaka, Go,Uozumi, Yasuhiro,Shimomura, Osamu,Ohtaka, Atsushi
, p. 57 - 61 (2021/11/13)
This paper describes the Suzuki Miyaura cross-coupling reaction of aryl bromides with potassium aryltrifluoroborates in water catalyzed by linear polystyrene-stabilized PdO nanoparticles (PSPdONPs). The reaction of aryl bromides having electron-withdrawing groups or electron-donating groups took place smoothly to give the corresponding coupling product in high yields. The catalyst recycles five times without significant loss of catalytic activity although a little bit increase in size of PdNPs was observed after the reaction.
New Nickel-Based Catalytic System with Pincer Pyrrole-Functionalized N-Heterocyclic Carbene as Ligand for Suzuki-Miyaura Cross-Coupling Reactions
Guo, Zhifo,Lei, Xiangyang
supporting information, (2021/09/11)
A new catalytic system with Ni(NO3)2·6H2O as the catalyst and a pincer pyrrole-functionalized N-heterocyclic carbene as the ligand was employed in the Suzuki-Miyaura cross-coupling reactions of aryl iodides with arylboronic acids. With 5 mol% catalyst, the catalytic reactions proceeded at 160 °C, giving coupling products in isolated yields of up to 94% in short reaction times (1-4 h). The system worked efficiently with aryl iodides bearing electron-donating or electron-withdrawing groups and arylboronic acids with electron-donating groups. Steric effects were observed for both aryl iodides and arylboronic acids. It is proposed that the reactions underwent a Ni(I)/Ni(III) catalytic cycle.
para-Selective arylation and alkenylation of monosubstituted arenes using thianthreneS-oxide as a transient mediator
Chen, Xiao-Yue,Nie, Xiao-Xue,Wu, Yichen,Wang, Peng
, p. 5058 - 5061 (2020/05/18)
Using thianthreneS-oxide (TTSO) as a transient mediator,para-arylation and alkenylation of mono-substituted arenes have been demonstratedviaapara-selective thianthrenation/Pd-catalyzed thio-Suzuki-Miyaura coupling sequence under mild conditions. This reaction features a broad substrate scope, and functional group and heterocycle tolerance. The versatility of this approach was further demonstrated by late-stage functionalization of complex bioactive scaffolds, and direct synthesis of some pharmaceuticals, including Tetriprofen, Ibuprofen, Bifonazole, and LJ570.
Preparation method of para-substituted aryl compound
-
, (2020/06/09)
The invention discloses a preparation method of a para-substituted aryl compound shown as a formula (I) which is described in the specfication. The preparation method is characterized by comprising the following step of: subjecting an aryl sulfonium salt shown as a formula (II) which is described in the specfication and boride to a coupling reaction in a solvent in an inert atmosphere under the action of alkali and a palladium catalyst to obtain the para-substituted aryl compound. According to the method, mono-substituted aromatic hydrocarbon is taken as a substrate, the aryl sulfonium salt isconstructed in situ, and the palladium catalyst catalyzes the aryl sulfonium salt constructed in situ to undergo the Suzuki-Miyaura coupling reaction, so a mono-substituted aromatic hydrocarbon para-arylation or alkenylation product is constructed quickly and efficiently. The method is mild in conditions, high in substrate universality and wide in tolerance of a heterocyclic coupling substrate.
4-Amino-1,2,4-triazoles-3-thiones and 1,3,4-oxadiazoles-2-thiones·palladium(II) recoverable complexes as catalysts in the sustainable Suzuki-Miyaura cross-coupling reaction
Chehrouri, Manel,Moreno-Cabrerizo, Cristina,Othman, Adil A.,Chabour, Ihssene,Ferrándiz-Saperas, Marcos,Sempere, Inmaculada,D?nda?, H. Ali,de Gracia Retamosa,Sansano, José M.
, (2020/08/05)
The Suzuki-Miyaura cross-coupling reaction using 4-amino-1,2,4-triazoles and 1,3,4-oxadiazoles-2-thiones·palladium (II) is studied. The reaction is optimized and the most appropriate catalytic complex is tested with several aryl halides, boronic acids in an environmentally benign solvent system (H2O/EtOH). The recovery of the catalytic species is also surveyed because of the nature of the employed solvent. A domino process is efficiently carried out following the standard conditions. Several surface parameters of the ligands are analyzed and the resulting values are extrapolated to the insoluble palladium catalyst.
Unified Protocol for Fe-Based Catalyzed Biaryl Cross-Couplings between Various Aryl Electrophiles and Aryl Grignard Reagents
Wang, Lei,Wei, Yi-Ming,Zhao, Yan,Duan, Xin-Fang
, p. 5176 - 5186 (2019/05/10)
The combination of commonly used FeCl3/SIPr with Ti(OEt)4/PhOM enabled a highly general iron-based catalyst system, which could efficiently catalyze the biaryl coupling reaction between various electrophiles (I, Br, Cl, OTs, OCONMe2, OSO2NMe2) and common or functionalized aryl Grignard reagents with high functional group tolerance. Selective couplings of aryl iodides and bromides over the corresponding oxygen-based electrophiles have been achieved, and thus a terphenyl acid intermediate for anidulafungin was conveniently synthesized via an orthogonal coupling strategy.
Schiff-based Pd(II)/Fe(III) bimetallic self-assembly monolayer—preparation, structure, catalytic dynamic and synergistic
Huang, Pingping,Song, Erran,Sun, Yimeng,Li, Tiesheng,Wei, Donghui,Liu, Minghua,Wu, Yangjie
, p. 75 - 86 (2019/03/13)
Graphene oxide supported Pd (II)/Fe (III) bimetallic catalytic monolayer (denoted as GO@H-Pd/Fe) was prepared and characterized. Its catalytic performances for Suzuki coupling reaction, synergetic effect and catalytic mechanism were systematic investigated. Results showed that orientation, composition and distribution of catalyst had efficient effect on catalytic activity. Catalytic activity of GO@H-Pd0.10/Fe0.90 was 475 times more than that of GO@H-Pd due to the ordered catalytic monolayer immobilized on GO, proper ratio of Pd/Fe and the synergetic effect between Pd(II) and Fe(III) which could form active cluster containing Pd and Fe. The Pd(II) could be made more negative by transferring electron from GO to Fe(III) via ligand and then to Pd, improving its catalytic activity since it was easy for oxide addition. It also exhibited better stability and recyclability at least 8 times due to proper functional ligand and support. Deactivation mechanism was confirmed to be the aggregation of active centre during the recycling. Heterogeneous catalytic mechanism was also proved by poison test, hot filtration and ReactIR. The results of ReactIR presented different dynamic catalytic process for GO@H-Pd0.10Fe0.90 and homogeneous catalyst (Li2PdCl4/FeCl3·6H2O).The activation energies were 9.7 KJ/mol and 3.7 KJ/mol obtained for heterogeneous and homogeneous catalyst, respectively. Considering the diffusion effect, the factor of supports on the activity was also investigated by ReactIR, with which that GO@H-Pd0.10Fe0.90 catalytic activity was higher than that of homogeneous catalyst could be confirmed.
