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991.
Dr. Wei-Ling Jiang Bin Huang Meng-Xiang Wu Ye-Kai Zhu Dr. Xiao-Li Zhao Prof. Dr. Xueliang Shi Prof. Dr. Hai-Bo Yang 《化学:亚洲杂志》2021,16(23):3985-3992
Metal-organic frameworks (MOFs) consisting of organic radicals are of great interest because they have exhibited unique and intriguing optical, electronic, magnetic, and chemo-catalytic properties, and thus have demonstrated great potential applications in optical, electronic, and magnetic devices, and as catalysts. However, the preparation of MOFs bearing stable organic radicals is very challenging because most organic radicals are highly reactive and difficult to incorporate into the framework of MOFs. Herein we reported a post-synthetic modification strategy to prepare a novel MOF containing phenazine radical cations, which was used as heterogeneous catalyst for aza-Diels-Alder reaction. The zinc-based metal-organic framework Zn2(PHZ)2(dabco) ( N ) was successfully synthesized from 5,10-di(4-benzoic acid)-5,10-dihydrophenazine (PHZ), triethylene diamine (dabco) with Zn(NO3)2 ⋅ 6H2O by solvothermal method. The as-synthesized MOF N was partially oxidized by AgSbF6 to form MOF R containing ∼10% phenazine radical cation species. The resultant MOF R was found to keep the original crystal type of N and very persistent under ambient conditions. Consequently, MOF R was successfully employed in radical cation-catalyzed aza-Diels-Alder reactions with various imine substrates at room temperature with high reaction conversion. Moreover, heterogeneous catalyst MOF R was reusable up to five times without much loss of catalytic activity, demonstrating its excellent stability and recyclability. Therefore, the post-synthetic modification developed in this work is expected to become a versatile strategy to prepare radical-based MOFs for the application of heterogeneous catalysts in organic synthesis. 相似文献
992.
利用滴定量热技术并结合适当的热力学循环测定了乙腈溶液中7个S-亚硝基-N-乙酰基-D,L-青霉胺二肽化合物中S—NO键的异裂能和均裂能, 其能量范围分别为234.5—246.2 kJ/mol和101.6—122.1 kJ/mol. 结果表明, 所研究的亚硝基硫醇化合物更容易通过S—NO键的均裂释放NO自由基(NO·). 通过热力学循环对7个亚硝基硫醇化合物自由基负离子中S—NO键的异裂能和均裂能进行估算, 能量范围分别为19.2—35.5 kJ/mol和-4.2—22.6 kJ/mol, 表明这些自由基负离子在室温下不稳定, 容易通过S—NO键的异裂释放出NO-. 相似文献
993.
A study has been conducted on the synthesis and characterization of a kind of novel polyrotaxanes comprisingα- cyclodextrins (α-CDs) threaded on triblock eopolymers with poly(ethylene glycol) (PEG) as a central axle and flanked by two low molecular weight polystyrenes as outer stoppers.Styrene was allowed to telomerize with polypseudorotaxanes as chain transfer agents made from the self-assembly of a distal thiol-capped PEG with a varying amount ofα-CDs in the presence of a redox initiation system at 40~C in aqueous solutions.The resulting polyrotaxanes were characterized in detail by ~1H-NMR,FTIR,XRD,TG and DSC analyses.The findings from the study demonstrated that the low molecular weight polystyrenes were successfully attached to two axle terminals of polypseudorotaxanes,and the number ofα-CDs threaded onto the PEG backbone was tunable by varying its molar feeding ratio to some extent,while the polymerization degree of PS nearly remained constant in this radical telomerization process. 相似文献
994.
Francesca Bellezza Renzo Ruzziconi Sara Spizzichino 《Journal of fluorine chemistry》2008,129(2):97-107
Regioselectively fluoro-, trifluoromethyl- and trifluoromethoxy-substituted 3-methyleneindolines have been prepared using a four-step procedure involving metalation/bromination of fluorinated Boc-protected anilines, N-propargylation of the resulting o-bromoarylcarbamate and reductive radical cyclization of the product with tributyltin hydride/AIBN. 3-Methyleneindolines, as valuable, versatile intermediates, can be transformed into highly functionalized 3-substituted indoles by ene-type reactions using different enophiles. Thus, fluoro-, trifluoromethyl- and trifluoromethoxy-substituted diethyl 2-hydroxy-2-[(1H-indol-3-yl)methyl]malonates, ethyl 2-hydroxy-3-(1H-indol-3-yl)propionates and ethyl 2-hydroxy-3-(1H-indol-3-yl)-2-trifluormethylpropionates were obtained in 77-86% yield by simply heating the corresponding tert-butyl 3-methyleneindoline-1-carboxylate with an equimolar amount of diethyl ketomalonate, ethyl glyoxalate and ethyl 3,3,3-trifluoropyruvate, respectively, at 100 °C, without solvent, for 0.5-4 h. 相似文献
995.
(PhSO2)2CFI was prepared in quantitative yield by the iodination of fluorobis(phenylsulfonyl)methane and utilized in facile radical bis(phenylsulfonyl)monofluoromethylation of various terminal alkenes. The synthetic methodology was further extended for the preparation of monofluoromethyl-substituted alkenes. 相似文献
996.
Leo Leung 《Journal of fluorine chemistry》2008,129(10):986-990
The AIBN-initiated addition of ethyl 4-iodo-2,2-difluoroacetate to a variety of alkene substrates is described. The addition generally led to the corresponding addition products in good to excellent yields and various functional groups could be tolerated under the reaction conditions. 相似文献
997.
Richard D. Adams Erin M. Boswell Shaobin Miao Charles Edwin Webster Michael B. Hall Narpinder Kaur 《Journal of organometallic chemistry》2008,693(16):2732-2738
Two new compounds CpFeMn2(CO)7(μ3-S2)2 (2) and Cp3Fe3Mn(CO)4(μ3-S2)2(μ3-S) (3) were obtained by the treatment of [CpFeMn(CO)5(μ3-S2)]2 (1) with CO at room temperature in the presence of room light. Compound 2 contains two triply bridging disulfido ligands on opposite sides of an open FeMn2 triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements show that it is paramagnetic with one unpaired electron per formula equivalent. The electronic structure of 2 was established by DFT and Fenske-Hall (FH) molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital that is located principally on the iron atom. The cyclic voltammogram of 2 exhibits one reversible one-electron oxidation wave at +0.34 V and one irreversible one-electron reduction wave at −0.66 V vs. Ag/AgCl. Compound 3 contains three iron atoms and one manganese atom with two triply bridging disulfido ligands and one triply bridging sulfido ligand and has no unpaired electrons. The molecular structures of compounds 2 and 3 were established by single crystal X-ray diffraction analyses. 相似文献
998.
Jacques Lalevée Nicolas Blanchard Xavier Allonas 《Journal of organometallic chemistry》2008,693(24):3643-3649
A comparison of the tris(trimethylsilyl)silyl I and tris(trimethylsilyl)germyl II radical reactivity is provided. Their formation as well as their reactivity encountered in a large variety of chemical processes (addition to double bond, halogen abstraction, peroxyl radical formation…) is examined by laser flash photolysis, quantum mechanical calculations and electron spin resonance (ESR) experiments. The starting compound (TMS)3GeH is more reactive than (TMS)3SiH toward the t-butoxyl, the t-butylperoxyl and the phosphinoyl radicals. A similar behavior is noted for an aromatic ketone triplet state. II exhibits a lower absolute electronegativity: accordingly, the addition to electron rich alkenes is less efficient than for I. Radical II is also found less reactive for both the peroxylation and the halogen abstraction reactions. The rearrangement of is slower than for ; this is related to the respective exothermicity of the processes. 相似文献
999.
CpCr(CO)3H and HV(CO)4(P-P) (where P-P is a chelating diphosphine) can be used to initiate radical cyclizations by transferring H to activated terminal olefins. CpCr(CO)3H can catalyze reductive cyclizations, with H2 as the ultimate reductant. Appropriate substrates can be assembled by the Morita-Baylis-Hillman reaction of methyl acrylate with an aldehyde. Six- as well as five-membered rings can be formed, and a tandem cyclization to decalin can be effected. 相似文献
1000.
Elena M. Sánchez 《Tetrahedron》2008,64(22):5111-5118
Sulfanyl radicals trigger a tandem addition-cyclization protocol in linalool or citronelene derivatives for the efficient construction of the iridane monoterpene skeleton. Best results in yields and diastereoselectivity were obtained when phenylethylsulfanyl was used as radical initiator. We have proved the utility of this protocol with the enantiospecific synthesis of natural iridane dehydroiridomyrmecin starting from a (−)-linalyl acetate ester derivative in five steps with a 28% overall yield. 相似文献