- Microwave-Accelerated C,N-Cyclometalation as a Route to Chloro-Bridged Iridium(III) Binuclear Precursors of Phosphorescent Materials: Optimization, Synthesis, and Studies of the Iridium(III) Dimer Behavior in Coordinating Solvents
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We present the results of our research on the use of microwaves as an unconventional heat source for the acceleration of iridium(III) chloro-bridged dimer preparation. The results enabled us to revise and improve known guidelines for the very quick and highly efficient synthesis of iridium(III) dimeric complexes in a very simple isolation manner. According to the developed methodology, the already known dimers containing ligands based on the 2-phenylpyridinato motif, as well as new ones stabilized with functionalized benzo[h]quinolinato and 2-phenoxypyridinato-based ligands, were efficiently synthesized. The scope of the incorporated ligands included compounds equipped with electron-donating (-Me,-OMe,-OPh,-NMe2), electron-withdrawing (-F,-Br,-CF3,-C6F5), and hole-transporting (-NPh2,-C6H4NPh2) groups. The obtained complexes were characterized by NMR, X-ray diffraction, and electrospray ionization mass spectrometry methods, and their behavior was examined in the presence of coordinating solvents such as dimethyl sulfoxide and acetonitrile. Investigation of the interactions between the above-mentioned solvents and dimers enabled us to confirm the ability of the former to cleave μ-chloride bridges, which enriches the knowledge in the field of organometallic chemistry. This knowledge can be particularly useful for the scientists working in the field of iridium-based materials, helping to avoid misinterpretation of the spectroscopic data.
- Januszewski, Rafa?,Kownacki, Ireneusz,Kubicki, MacIej,Oh, Myong Joon,Orwat, Bartosz,Zaranek, MacIej
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- Ruthenium-Catalyzed meta-CAr–H Bond Difluoroalkylation of 2-Phenoxypyridines
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A ruthenium-catalyzed meta-selective CAr–H bond difluoroalkylation of 2-phenoxypyridine using 2-bromo-2,2-difluoroacetate has been developed. Mechanistic studies indicated that this difluoroalkylation might involve a radical process. Furthermore, a new method is reported for the synthesis of 2-(meta-difluoroalkylphenoxy)pyridine derivatives, which are present in many pharmaceuticals and other functional compounds.
- Jia, Chunqi,Wang, Shichong,Lv, Xulu,Li, Gang,Zhong, Lei,Zou, Lei,Cui, Xiuling
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supporting information
p. 1992 - 1995
(2020/03/23)
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- Substituent Effects of 2-Pyridones on Selective O-Arylation with Diaryliodonium Salts: Synthesis of 2-Aryloxypyridines under Transition-Metal-Free Conditions
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An efficient transition-metal-free strategy to synthesize 2-aryloxypyridine derivatives has been developed by a selective O-arylation of 2-pyridones with diaryliodonium salts. The reaction was compatible with a series of functional groups for 2-pyridones and diaryliodonium salts such as halides, nitro, cyano, and ester groups. The substituents at the C6-position of 2-pyridones favored O-arylation products because of steric hindrance. The reaction was easily performed on a gram-scale and 6-chloro-2-pyridone was a good precursor to access various unsubstituted 2-aryloxypyridines by dehalogenation. A P2Y 1 lead compound analogue could be prepared in good yield over two steps.
- Li, Xiao-Hua,Ye, Ai-Hui,Liang, Cui,Mo, Dong-Liang
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p. 1699 - 1710
(2018/02/06)
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- Cycloauration of substituted 2-phenoxypyridine derivatives and X-ray crystal structure of gold, dichloro[2-[[5-[(cyclopentylamino) carbonyl]-2-pyridinyl-κN]oxy]phenyl-κC]-, (SP-4-3)-
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Direct cycloauration of 2-phenoxypyridines with different substituents at the 5-position of the pyridine ring was carried out in an CH3CN/H2O medium, leading to isolation of cycloaurated compounds AuCl2(L) (HL = substitute
- Zhu, Yongbao,Cameron, Beth R.,Skerlj, Renato T.
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- SYNTHESIS OF PHENOXYPYRIDINES UNDER PHASE TRANSFER CATALYSIS CONDITIONS
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Reactions of halopyridines with alkali metal phenoxides in a two phase liquid-solid catalytic system, rather than in a liquid-liquid phase transfer catalytic system, make it possible to prepare 2-, 3-, and 4-phenoxypyridines from unactivated bromo- or chloropyridines and 2-chloropicolines.In polyhalogenated pyridines only α- and γ-halogen atoms undergo substitution. 7,8-Dibromo-6-azaphenoxane has been prepared by the reaction of 2,3,5,6-tetrabromopyridine with the dipotassium salt of pyrocatechol.
- Abele, E. M.,Gol'dberg, Yu. Sh.,Gavars, M. P.,Gaukhman, A. P.,Shimanskaya, M. V.
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p. 290 - 294
(2007/10/02)
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- The Structure-Reactivity-Chemoselectivity Relationship on the Reactions of 1-Unsubstituted Tautomeric 2-Pyridones with Benzyne
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The reactions of 2-pyridones with benzyne were investigated in order to gain some insight into the structure-reactivity-chemoselectivity relatinoship involved in the tautomeric systems.All reactions examined have resulted in the formation of Diels-Alder and Michael-type adducts.It has been shown that the Diels-Alder reactivities were well correlated with the HOMO energy levels of the 2-pyridone form and the yields of the Michael-type adduct were closely associated with the tautomeric equilibria.In summary, the chemoselectivities of 2-pyridones in the reaction with benzyne were largely affected by the tautomeric properties.
- Kuzuya, Masayuki,Noguchi, Akihiro,Mano, Ei-ichi,Okuda, Takachiyo
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p. 1149 - 1155
(2007/10/02)
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