- Synthesis of thioethers, arenes and arylated benzoxazoles by transformation of the C(aryl)-C bond of aryl alcohols
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Transformation of aryl alcohols into high-value functionalized aromatic compounds by selective cleavage and functionalization of the C(aryl)-C(OH) bond is of crucial importance, but very challenging by far. Herein, for the first time, we report a novel and versatile strategy for activation and functionalization of C(aryl)-C(OH) bonds by the cooperation of oxygenation and decarboxylative functionalization. A diverse range of aryl alcohol substrates were employed as arylation reagents via the cleavage of C(aryl)-C(OH) bonds and effectively converted into corresponding thioether, arene, and arylated benzoxazole products in excellent yields, in a Cu based catalytic system using O2 as the oxidant. This study offers a new way for aryl alcohol conversion and potentially offers a new opportunity to produce high-value functionalized aromatics from renewable feedstocks such as lignin which features abundant C(aryl)-C(OH) bonds in its linkages.
- Chen, Bingfeng,Han, Buxing,Liu, Mingyang,Meng, Qinglei,Song, Jinliang,Zhang, Pei,Zhang, Zhanrong
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p. 7634 - 7640
(2020/08/14)
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- Metal-Free Aerobic Oxidation of Nitro-Substituted Alkylarenes to Carboxylic Acids or Benzyl Alcohols Promoted by NaOH
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Efficient and selective aerobic oxidation of nitro-substituted alkylarenes to functional compounds is a fundamental process that remains a challenge. Here, we report a metal-free, efficient, and practical approach for the direct and selective aerobic oxidation of nitro-substituted alkylarenes to carboxylic acids or benzyl alcohols. This sustainable system uses O2 as clean oxidant in a cheap and green NaOH/EtOH mixture. The position and type of substituent critically affect the products. In addition, this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities. Finally, the reactions can be conducted in a pressure reactor, which can conserve oxygen and prevent solvent loss. The approach was conducive to environmental protection and potential industrial application.
- Fang, Kun,Li, Guijie,She, Yuanbin
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p. 8092 - 8103
(2018/06/25)
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- Method for preparing nitro aromatic acid/nitro alpha-aryl alcohol through oxidizing substituted alkyl nitrobenzene by oxygen
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A method for preparing nitro aromatic acid/nitro alpha-aryl alcohol through oxidizing substituted alkyl nitrobenzene by oxygen comprises the following steps: taking substituted alkyl nitrobenzene shown as the formula (1) as a raw material, oxygen as an oxidizing agent and sodium hydroxide as an alkaline substance, mixing in a solvent uniformly, reacting for 3 to 24h at the temperature of 25 to 65 DEG C, and treating obtained reaction liquid to obtain the nitro aromatic acid or nitro alpha-aryl alcohol; the mass ratio of the substituted alkyl nitrobenzene to the sodium hydroxide is 1 to (2 to 10) and the oxygen pressure is 0.1 to 2.0 MPa. The method provided by the invention has the advantages that a catalyst is not needed, the raw material is low in price and easy to recycle, the reaction temperature is moderate, the production and control are easy; the raw material transformation rate is high; the target product selectivity is high, the yield is up to 91%, and the application prospect is wide. The formula (1) is shown in the description.
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Paragraph 0094; 0095; 0096
(2017/09/01)
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- From in vitro to in cellulo: Structure-activity relationship of (2-nitrophenyl)methanol derivatives as inhibitors of PqsD in Pseudomonas aeruginosa
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Recent studies have shown that compounds based on a (2-nitrophenyl)methanol scaffold are promising inhibitors of PqsD, a key enzyme of signal molecule biosynthesis in the cell-to-cell communication of Pseudomonas aeruginosa. The most promising molecule displayed anti-biofilm activity and a tight-binding mode of action. Herein, we report on the convenient synthesis and biochemical evaluation of a comprehensive series of (2-nitrophenyl)methanol derivatives. The in vitro potency of these inhibitors against recombinant PqsD as well as the effect of selected compounds on the production of the signal molecules HHQ and PQS in P. aeruginosa were examined. The gathered data allowed the establishment of a structure-activity relationship, which was used to design fluorescent inhibitors, and finally, led to the discovery of (2-nitrophenyl)methanol derivatives with improved in cellulo efficacy providing new perspectives towards the application of PqsD inhibitors as anti-infectives. This journal is the Partner Organisations 2014.
- Storz, Michael P.,Allegretta, Giuseppe,Kirsch, Benjamin,Empting, Martin,Hartmann, Rolf W.
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supporting information
p. 6094 - 6104
(2014/08/05)
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- Acetyl-BINOL as mimic for chiral β-diketonates: A building block for new modular ligands
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α-Acetyl-(S)-BINOL was prepared by ortho-lithiation and subsequent acetylation of acetal-protected (S)-BINOL. The β-hydroxyketone moiety of this compound is herein a structural mimic for a β-diketonate and forms six-membered chelates with transition metal ions. The second hydroxy-function was submitted to esterification with several carboxylic acids bearing another donor function, thus, new tridentate chiral ligands were obtained. Out of this library the l-proline-α-acetyl-(S)-BINOL-ester was identified to be most effective for the titanium-mediated addition of Et2Zn to PhCHO yielding the respective secondary alcohol with up to 93% ee, which is better than with using (S)-BINOL itself. Besides a solvent dependency (use of MeCN is optimal), the proper choice of the counter-ion is crucial: anion exchange of bromide by trifluoroacetate gave a significant increase of enantioselectivity. Copyright
- Von R?nn, Robert,Christoffers, Jens
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scheme or table
p. 334 - 338
(2011/03/18)
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- MERCURATION OF ALKYLCYCLOPROPANES WITH ELECTRON-ACCEPTING SUBSTITUENTS IN THE AROMATIC RING
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The reactions of (nitrophenyl)- and (acetylphenyl)cyclopropanes with mercuric nitrate and acetate in methanol, acetic acid, and formic acid were studied.The arylcyclopropanes are mercurated by mercuric acetate in formic acid or by mercuric nitrate in all the employed solvents without a catalyst (perchloric acid).A relatively high rate of conjugate mercuration of arylcyclopropanes in formic acid was observed.
- Bandaev, S. G.,Eshnazarov, Yu. Kh.,Nasyrov, I. M.,Mochalov, S. S.,Shabarov, Yu. S.
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p. 659 - 663
(2007/10/02)
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