- Multi-stimuli-responsive fluorescence of axially chiral 4-ene-β-Diketones
-
A unique series of simple, smart, and chiral binaphthalene-substituted 4-ene-β-diketones molecules has been designed and prepared. Their optical properties, charge contribution, and transition process highly depend on their chemical structures. These π-conjugated materials are highly emissive in both solution and solid (emission quantum yield up to 68%), owing to the inhibition of enol-keto tautomerization and the effect of steric hindrance from binaphthalene. Through ethylenic bond hydrolysis, they can be used for not only cation/anion sensing but also chiral amino acids recognition. Moreover, at low concentrations, they have little cytotoxicity to living cells and can stain cytoplasm. Therefore, they afford a new platform in the design of multi-stimuli-responsive, smart, and chiral materials.
- Wu, Dehua,Fang, Xinyi,Song, Jintong,Qu, Lang,Zhou, Xiangge,Xiang, Haifeng,Wang, Jun,Liu, Jin
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-
- Photoinduced Diverse Reactivity of Diazo Compounds with Nitrosoarenes
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A diverse reactivity of diazo compounds with nitrosoarene in an oxygen-transfer process and a formal [2 + 2] cycloaddition is reported. Nitosoarene has been exploited as a mild oxygen source to oxidize an in situ generated carbene intermediate under visible-light irradiation. UV-light-mediated in situ generated ketenes react with nitosoarenes to deliver oxazetidine derivatives. These operationally simple processes exemplify a transition-metal-free and catalyst-free protocol to give structurally diverse α-ketoesters or oxazetidines.
- Roy, Sourav,Kumar, Gourav,Chatterjee, Indranil
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supporting information
p. 6709 - 6713
(2021/09/08)
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- Discovery of pyrazole N-aryl sulfonate: A novel and highly potent cyclooxygenase-2 (COX-2) selective inhibitors
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Based on a new pyrazole sulfonate synthetic method, a novel class of molecules with a basic structure of pyrazole N-aryl sulfonate have been designed and synthesized. The interest in conducting intensive research stems from quite evident anti-inflammatory effects exhibited by the compounds in preliminary animal experiments. A series of compounds were synthesized by different substitutions of the R1, R2, and R3 groups. Within the series, 4-iodophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and phenyl 5-methyl-3-(4-(trifluoromethyl) phenyl)-1H-pyrazole-1-sulfonate exhibited excellent anti-inflammatory activity (% inhibition of auricular edemas = 27.0 and 35.9, respectively); the in vivo analgesic activity of phenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and 2-chlorophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate was confirmed to be effective (inhibition ratio of writhing = 50.7% and 48.5% separately), and compounds phenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate, 4-iodophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and 2-chlorophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate were identified as selective COX-2 inhibitors (SI = 455, 10,497 and >189 severally). In Acute Oral Toxicity assays conducted in vivo, the lethal dose 50 (LD50) of 4-iodophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and 2-chlorophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate to mice was >2000 mg/kg BW.
- Guo, Quanping,Wang, Mengran,Wang, Rui,Xu, Zhaoqing,Yao, Haiyan
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-
- Allenone-Mediated Racemization/Epimerization-Free Peptide Bond Formation and Its Application in Peptide Synthesis
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Allenone has been identified as a highly effective peptide coupling reagent for the first time. The peptide bond was formed with an α-carbonyl vinyl ester as the key intermediate, the formation and subsequent aminolysis of which proceed spontaneously in a racemization-/epimerization-free manner. The allenone coupling reagent not only is effective for the synthesis of simple amides and dipeptides but is also amenable to peptide fragment condensation and solid-phase peptide synthesis (SPPS). The robustness of the allenone-mediated peptide bond formation was showcased incisively by the synthesis of carfilzomib, which involved a rare racemization-/epimerization-free N to C peptide elongation strategy. Furthermore, the successful synthesis of the model difficult peptide ACP (65-74) on a solid support suggested that this method was compatible with SPPS. This method combines the advantages of conventional active esters and coupling reagents, while overcoming the disadvantages of both strategies. Thus, this allenone-mediated peptide bond formation strategy represents a disruptive innovation in peptide synthesis.
- Wang, Penghui,Wang, Xuewei,Wang, Zhengning,Zhao, Junfeng
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p. 10374 - 10381
(2021/07/26)
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- Synthesis of Highly Substituted Biaryls by the Construction of a Benzene Ring via in Situ Formed Acetals
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Herein, we present an interesting method for the construction of a benzene ring using propargylic alcohols and 1,3-dicarbonyls, which involves three new C-C bond formations via cascade alkylation, formylation, annulation, and aromatization to make substituted biaryls. This one-pot Br?nsted acid-promoted protocol utilizes the unique reactivity of the acetal formed under the reaction conditions. Alkynyl methyl ketones could be employed instead of 1,3-dicarbonyls as they are converted to 1,3-dicarbonyls by hydration under the reaction conditions.
- Balamurugan, Rengarajan,Manojveer, Seetharaman,Tarigopula, Chandrahas
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p. 11871 - 11883
(2021/09/13)
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- Ag-Catalyzed Insertion of Alkynyl Carbenes into C-C Bonds of β-Ketocarbonyls: A Formal C(sp2) Insertion
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Here we report a silver-catalyzed alkynyl carbene insertion into β-ketocarbonyls using alkynyl N-nosylhydrazones as alkynyl carbene precursors, which provides access to trisubstituted allenyl ketones. This reaction represents the first example of an alkynyl carbene insertion into a C-C σ bond, affording products homologated with an sp2 carbon center. The products are useful substrates for further transformations. Experimental investigations and theoretical calculations suggest the reaction proceeds through a stepwise enol cyclopropanation/retro-aldol pathway.
- Anderson, Edward A.,Bi, Xihe,Ning, Yongquan,Sivaguru, Paramasivam,Song, Qingmin,Wu, Lizuo
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supporting information
(2022/01/20)
-
- 1-phenylazoacetylacetone chelate, and preparation method and application thereof
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The invention relates to the technical field of polymer solar cells, and in particular relates to a 1-phenylazoacetylacetone chelate, and a preparation method and application thereof. The 1-phenylazoacetylacetone chelate has the structure as shown in the formula (I); in the formula (I), M is selected from any metal element in the group IIIA or any metal element in the group IIIB; the 1-phenylazoacetylacetone chelate is used as the material of an electron transfer layer, and used in a polymer solar cell device; compared with other electron transfer layers, the 1-phenylazoacetylacetone chelate can form a certain hemispherical structure on the surface of an active layer while having excellent transfer capability; the path of the incident light is increased; simultaneously, after the thicknessis reasonably controlled, the maximum intensity in the device is at the position of the active layer; the enhanced light of the active layer is absorbed; therefore, the exciton generation rate is increased; and the short-circuit current density and the photoelectric conversion efficiency of a battery device are increased.
- -
-
Paragraph 0135-0137
(2020/12/08)
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- Direct synthesis of 2,3,5-trisubstituted pyrroles: via copper-mediated one-pot multicomponent reaction
-
We have developed a copper-mediated one-pot synthesis of 2,3,5-trisubstituted pyrroles from 1,3-dicarbonyl compounds and acrylates using ammonium acetate as a nitrogen source. The reaction achieves C-C and C-N bond formation and provides an efficient approach to access highly functionalized pyrroles without further raw material preparation. This method is operationally simple, compatible with a wide range of functional groups, and provides the target products in moderate to good yields. This journal is
- He, Jian-Ping,Huang, Guo-Sheng,Luo, Nan,Zhan, Zhen-Zhen,Zhang, Ming-Ming
-
supporting information
p. 9831 - 9835
(2021/01/05)
-
- Pyrazoles: 'one-pot' synthesis from arenes and carboxylic acids
-
A rapid and efficient method for 'one-pot' synthesis of pyrazoles from (hetero)arenes and carboxylic acids via successive formation of ketones and β-diketones followed by heterocyclization with hydrazine has been developed. The utility of the RCOOH/TfOH/TFAA acylation system for intermediate production of ketones and 1,3-diketones is a key feature of this approach. The preliminary evaluation of the anticancer activity of the synthesized pyrazoles is performed.
- Gong, Ming,Kim, Jung Keun,Kovalev, Vladimir V.,Kovaleva, Olga V.,Shokova, Elvira A.,Tafeenko, Viktor A.,Wu, Yangjie
-
supporting information
p. 5625 - 5638
(2020/08/21)
-
- A General Proline-Catalyzed Synthesis of 4,5-Disubstituted N-Sulfonyl-1,2,3-Triazoles from 1,3-Dicarbonyl Compounds and Sulfonyl Azide
-
An efficient proline-catalyzed synthesis of 4,5-disubstituted-N-sulfonyl-1,2,3-triazoles has been accomplished from 1,3-dicarbonyl compounds and sulfonyl azides. The developed reaction is suitable for various symmetrical and unsymmetrical 1,3-dicarbonyl compounds, tolerates various functional groups and affords 4,5-disubstituted-N-sulfonyl-1,2,3-triazoles in good yield with excellent regioselectivity. Rhodium-catalyzed denitrogenative functionalization of 4,5-disubstituted-N-sulfonyl-1,2,3-triazoles further demonstrates their utility in organic synthesis.
- Rajasekar, Shanmugam,Anbarasan, Pazhamalai
-
supporting information
p. 4563 - 4567
(2019/11/03)
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- Method of preparing 1,3-diketone compound by acetyenic ketone
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The invention relates to a preparation method of preparing a 1,3-diketone compound by acetyenic ketone. The preparation method comprises the following steps: S1, putting alpha-alkynyl ketone compound,water, gold salt and silver salt in a reaction solvent to obtain a precursor mixture, wherein the molar ratio of the alpha-alkynyl ketone compound, water, gold salt and silver salt is 1: (1-50): (0.001-0.10): (0.002-0.15); and S2, putting the precursor mixture obtained in the S1 to react at a reaction temperature of 0-50 DEG C to obtain the 1,3-diketone compound, wherein the reaction time is 5 min to 48 h. The method is simple in reaction condition, free of acid or alkaline additives and high in yield, and can be applied to modern production on a large scale.
- -
-
Paragraph 0120-0125
(2019/06/12)
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- ONE-STEP, FAST, 18F-19F ISOTOPIC EXCHANGE RADIOLABELING OF DIFLUORO-DIOXABORININS AND USE OF SUCH COMPOUNDS IN TREATMENT
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A compound according to Formula (I) or a pharmaceutically acceptable salt and/or solvate thereof, wherein X1 and X2 are each independently 18F or 19F; R1 and R2 are each independently alkyl, amine, perfluoroalkyl, alkenyl, alkynyl, aryl, or aralkenyl; and R3 is H, halo, alkyl, alkyl ester, alkenyl, alkynyl, aryl, or aralkenyl; or wherein: R1 and R3 or R2 and R3 join to form a 6-membered cycloalkyl or heterocyclyl; or R1 and R3, R2 and R3, or R1, R2, and R3 join to form a substituted or unsubstituted polycyclic ring, wherein the polycyclic ring comprises fused cycloalkyl, heterocycloalkyl, aryl, or heteroaryl rings.
- -
-
Paragraph 0019; 0204-0205
(2019/12/15)
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- Mild Cu-Catalyzed Oxidation of Benzylic Boronic Esters to Ketones
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The oxidation of benzylic boronic esters directly to the ketone is reported. This mild Cu-catalyzed method uses an ambient atmosphere of air as the terminal oxidant and is notably chemoselective. Oxidation of the C-B bond occurs selectively, even in the presence of unprotected alcohols. Initial investigation suggests the reaction proceeds through an alkylboron to Cu transmetalation, peroxide formation, and rearrangement to give the carbonyl.
- Grayson, James D.,Partridge, Benjamin M.
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p. 4296 - 4301
(2019/05/14)
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- Design, synthesis and biological evaluation of substituted 2-amino-1,3-thiazine derivatives as antituberculosis and anti-cancer agents
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A series of substituted 2-amino-1,3-thiazines were synthesized as amides (9a–9i), carbamates (9j–9m), sulfonamides (9n–9o) and urea derivatives (9p–9q) by treating the compound 7 with acid chlorides (8a–8i), chloroformates (8j–8m), sulfonyl chlorides (8n–8o) and isocyanates (8p–8q) respectively. The synthesized compounds (9a–9q) were screened for antituberculosis activity against Mycobacterium tuberculosis H37Rv ATCC 27294 and the results show that some of these derivatives possess good activity against Mycobacterium tuberculosis H37Rv ATCC 27294. A few also display promising cytotoxic activity against human breast cancer MCF-7 and human esophageal cancer EC-9706 cell lines. Regarding both biological profiles 9b, 9m and 9h are the most active for anti-cancer, anti-TB activity.
- Nagendra Prasad, Tangella,Eeda, Koti Reddy,Gudise, Veera Babu,Basha, Shaik Firoj,Anwar, Shaik
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supporting information
p. 1277 - 1285
(2019/04/27)
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- Pyrazole compound containing N-aryl sulfonate and synthesis and application thereof
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The invention discloses a pyrazole compound containing N-aryl sulfonate. A structural formula of the pyrazole compound is shown in the description. Proofed by pharmacological study, the pyrazole compound has the advantages that the activity of cyclooxygenase 2 is inhibited; the high-efficiency inhibition function on the generation of cyclooxygenase 2 due to inflammation mediums is realized, so that the pyrazole compound can be used as an active matter, and the prepared anti-inflammation medicine can be used for treating the inflammations, such as rheumatic arthritis and rheumatalgia, and the diseases and symptoms, such as fevers.
- -
-
Paragraph 0038
(2018/07/10)
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- Rhodium(ii)-catalysed generation of cycloprop-1-en-1-yl ketones and their rearrangement to 5-aryl-2-siloxyfurans
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Donor-acceptor cyclopropenes formed from enoldiazoketones undergo catalytic rearrangement to 5-aryl-2-siloxyfurans via a novel mechanism that involves a nucleophilic addition of the carbonyl oxygen to the rhodium-activated cyclopropene.
- Marichev, Kostiantyn O.,Wang, Yi,Carranco, Alejandra M.,Garcia, Estevan C.,Yu, Zhi-Xiang,Doyle, Michael P.
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p. 9513 - 9516
(2018/08/28)
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- Vinyl nosylates as partner in copper and silver co-catalyzed Sonogashira cross-coupling reactions
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Vinyl nosylates, readily obtained from β-dicarbonyl derivatives, could be efficiently engaged in Sonogashira cross-coupling reactions, either cocatalyzed by copper or silver salts. The para-nitrobenzenesulfonate (nosylate) group allows this coupling to be performed under very mild conditions (room temperature). These new leaving group and mild conditions could be applied to the synthesis of acetylenic coumarinyl derivatives and to the total synthesis of an acetylenic monoterpene natural product, named cleviolide.
- Cheval, Nicolas P.,Hoffmann, Barbara,Dikova, Anna,Sirindil, Fatih,Bertus, Philippe,Blanc, Aurélien,Weibel, Jean-Marc,Pale, Patrick
-
supporting information
p. 7111 - 7119
(2018/11/10)
-
- Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
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A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
- Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
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p. 3275 - 3284
(2018/03/25)
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- Preparation method of aromatic ketone
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The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
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Paragraph 0051; 0052; 0053; 0055
(2018/09/11)
-
- Wacker-Type Oxidation Using an Iron Catalyst and Ambient Air: Application to Late-Stage Oxidation of Complex Molecules
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A practical and general iron-catalyzed Wacker-type oxidation of olefins to ketones is presented, and it uses ambient air as the sole oxidant. The mild oxidation conditions enable exceptional functional-group tolerance, which has not been demonstrated for any other Wacker-type reaction to date. The inexpensive and nontoxic reagents [iron(II) chloride, polymethylhydrosiloxane, and air] can, therefore, also be employed to oxidize complex natural-product-derived and polyfunctionalized molecules.
- Liu, Binbin,Jin, Fengli,Wang, Tianjiao,Yuan, Xiaorong,Han, Wei
-
supporting information
p. 12712 - 12717
(2017/09/11)
-
- 2-oxadiazole-3-aminothiophene thieno-[2,3-b] pyridine derivative and preparing method and application thereof
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The invention belongs to the field of chemical pharmaceuticals, and particularly relates to a 2-oxadiazole-3-aminothiophene thieno-[2,3-b] pyridine derivative and a preparing method and application thereof. The structure of the 2-oxadiazole-3-aminothiophene thieno-[2,3-b] pyridine derivative is shown in the formula I. A compound of the 2-oxadiazole-3-aminothiophene thieno-[2,3-b] pyridine derivative has the good HCV inhibitory effect, and meanwhile shows the low cytotoxicity, and a new method is provided for development of an anti-HCV inhibitor. The general formula is defined in the description.
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-
Paragraph 0066-0068
(2017/09/01)
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- Β-carbonyl enamines compound and as the application of the preparation of plant pathogenic bacteria antibacterial agent (by machine translation)
-
The invention relates to a β-carbonyl compound and enamines preparation of plant pathogenic bacteria as the application of an antimicrobial agent. Commercially available antibacterial agent Mijunzhi as a positive control, the linear growth of the mycelium determination process 23 kind of target compound anthrax pathogenicbacteria the apple, corn curved spore pathogenic bacterium, pathogenic bacteria rice blast fungus, reducing bakanae disease of wheat, such as watermelon blighting pathogenicbacteria 5 common inhibiting activity of plant pathogenic fungi, the result shows that: the target compound has tries the fungus inhibiting effect of different degree. Compound 8, 11, 12, 14, 16 of the activity is better, for the majority of their pathogenic bacteria testing EC 50 half of the effect of the concentration value is higher than the positive control drug kresoxim-methyl. Especially compound 8 inhibition of anthrax pathogenicbacteria the apple active (EC 50 = 2.15μg/mL) compound and 12 the inhibitory activity of pathogenic bacterium curved spore (EC 50 = 9.14μg/mL) are Mijunzhi active (EC 50 = 15.45 & 76.06μg/mL) of 8 times, has potential development and application values. (by machine translation)
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Paragraph 0051; 0052; 0053; 0054; 0055
(2016/10/08)
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- Dendrimer-like core cross-linked micelle stabilized ultra-small gold nanoclusters as a robust catalyst for aerobic oxidation of α-hydroxy ketones in water
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As one of the most general and promising stabilizers, dendrimers have been widely used to prepare ultra-small gold nanoclusters. However, the complex synthesis of dendrimers hinders the further application of protected nanoclusters. Here we report a facile strategy to prepare an alternative material via core cross-linking of self-assembled micelles. The resulting dendrimer-like core cross-linked micelles (DCCMs) retain the main characteristics of dendrimers and avoid complex chemical synthesis. As expected, the DCCMs could easily encapsulate gold nanoparticles within their cores. The ultra-small clusters of Au5 were prepared without the participation of external reductants. Importantly, the DCCM stabilized noble gold clusters furnish excellent catalytic activity and perfect reusability for aerobic oxidation of α-hydroxy ketones in water. Only in open air the oxidation could be repeated up to 48 times with negligible turn-over frequency change. The total turnover number (TON) of the reaction reached unexpectedly >48 000, the highest TON for metal catalysed oxidation of hydroxy ketones so far. The further mechanism study hints that the carboxylic group of substrates might be involved in the catalytic process. The simple catalyst preparation, the environmentally benign reaction conditions, and the excellent catalytic performance and durability make the novel DCCM protected gold nanocluster a green catalyst.
- Yu, Yangyang,Lin, Chenlu,Li, Bing,Zhao, Pengxiang,Zhang, Shiyong
-
supporting information
p. 3647 - 3655
(2016/07/06)
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- A 1,3-diones substitution alkone method of synthesizing α-
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The invention discloses a method for synthesizing alpha-substituted ketone by using a 1,3-diketone compound, and belongs to the field of preparation of fine chemical engineering. The 1,3-diketone compound with an electron-withdrawing substituent group at 2-position is used as a substrate, an accelerant is added, and alpha-substituted ketone is synthesized by utilizing mixed solvent of tetrahydrofuran and water. An efficient and single method for synthesizing the alpha-substituted ketone, which is mild in condition, low in cost and suitable for large-scale production is provided.
- -
-
Paragraph 0067; 0068; 0069; 0070; 0071; 0072
(2016/10/10)
-
- Ene di- and trimerization of 1-methyl-2-phenylcyclopropene
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1,2-Disubstituted cyclopropene, 1-methyl-2-phenylcyclopropene (18), was generated by bromo-lithium exchange of 1-bromo-2-phenylcyclopropene followed by treatment with methyl iodide. Compound 18 was oxidized by oxygen to give the α,β-unsaturated carbonyl product 25 and diketone 27 and the tautomeric, β-hydroxyl-α,β-unsaturated ketone 28. However, compound 28 reacted further with the cyclopropene 18 in a retro-Claisen-like reaction to generate adduct 26. Furthermore, compound 18 underwent ene dimerization in neat condition to form the endo-dimer 40 and exo-dimer 41 followed by oxidization with oxygen to give aldehyde 39. It is noteworthy that the endo-dimer 40 and exo-dimer 41 could be trapped with thiophenol to give adduct 42 and 43. In addition, the ene reaction of exo-dimer 41 with monomer 18 gave an exo-exo ene trimer 46 through an exo-transition state which was also trapped by thiophenol to give adducts 44 and 45.
- Lin, Hung-Chun,Tsai, Ru-Ting,Wu, Hsiao-Pin,Lee, Hsin-Yi,Lee, Gon-Ann
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p. 184 - 191
(2015/12/23)
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- Highly enantioselective Michael addition of 2-fluoro-1,3-diketones to nitroalkenes
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Highly enantioselective Michael addition of 2-fluoro-1,3 diketones to nitroalkenes was developed, and the desired adducts were obtained in good chemical yields with moderate to good diastereoselectivties and excellent enantioselectivities. Subsequent stereoselective reduction of the carbonyl groups led to the preparation of a functionalized fluoroisostere of glycerol that contains four continuous stereogenic centers.
- Kwiatkowski, Jacek,Lu, Yixin
-
supporting information
p. 320 - 324
(2015/02/19)
-
- Synthesis and biological evaluation of 3-alkyl-1,5-diaryl-1H-pyrazoles as rigid analogues of combretastatin A-4 with potent antiproliferative activity
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A series of novel 3-alkyl-1,5-diaryl-1H-pyrazoles were synthesized as combretastatin A-4 (CA-4) analogues and evaluated for antiproliferative activity against three human cancer cell lines (SGC-7901, A549 and HT-1080). Most of the target compounds displayed moderate to potent antiproliferative activity, and 7k was found to be the most potent compound. Structure-activity relationships indicated that compounds with a trimethoxyphenyl A-ring at the N-1 position of the pyrazole skeleton were more potent than those with the A-ring at the C-5 position. Tubulin polymerization and immunostaining experiments revealed that 7k potently inhibited tubulin polymerization and disrupted tubulin microtubule dynamics in a manner similar to CA-4. Computational modelling demonstrated that the binding of 7k to the colchicine binding site on microtubules may involve a similar mode as CA-4.
- Xu, Qile,Qi, Huan,Sun, Maolin,Zuo, Daiying,Jiang, Xuewei,Wen, Zhiyong,Wang, Zhiwei,Wu, Yingliang,Zhang, Weige
-
-
- A chemoselective α-aminoxylation of aryl ketones: a cross dehydrogenative coupling reaction catalysed by Bu4NI
-
Tetrabutyl ammonium iodide (TBAI) catalyzed α-aminoxylation of ketones using aq. TBHP as an oxidant has been accomplished. We have shown that the CDC (cross dehydrogenative coupling) reactions of ketones with N-hydroxyimidates such as N-hydroxysuccinimide (NHSI), N-hydroxyphthalimide (NHPI), N-hydroxybenzotriazole (HOBt) and 1-hydroxy-7-azabenzotriazole (HOAt) lead to the corresponding oxygenated products in good to moderate yields. The application of this method has been demonstrated by transforming a few coupled products into synthetically useful intermediates and products.
- Siddaraju, Yogesh,Prabhu, Kandikere Ramaiah
-
supporting information
p. 11651 - 11656
(2015/12/08)
-
- Direct synthesis of 1,3-dicarbonyl compounds via radical coupling of aldehydes with ketones under metal-free conditions
-
An efficient approach for the synthesis of 1,3-diketones from aldehydes and ketones has been developed using Bu4NI (TBAI) as the catalyst. In the presence of DTBP-TBHP/p-TsOH, aldehydes undergo radical coupling with ketones to provide the desired products in moderate to high yields at 120 °C. Although various substituents on the aromatic ring of aldehydes are well tolerable under the standard reaction conditions, the protocol is limited by the scope of ketones. The method exhibits advantages in terms of the easy access of the starting materials, operational simplicity, functional group tolerance, and the absence of metal catalyst.
- Shen, Xuqian,Borah, Arun Jyoti,Cao, Xihan,Pan, Weixiang,Yan, Guobing,Wu, Xiangmei
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p. 6484 - 6487
(2015/11/16)
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- Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones
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A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.
- He, Zhen,Qi, Xiaotian,Li, Shiqing,Zhao, Yinsong,Gao, Ge,Lan, Yu,Wu, Yiwei,Lan, Jingbo,You, Jingsong
-
supporting information
p. 855 - 859
(2015/02/05)
-
- Discovery and structure-activity relationships study of novel thieno[2,3-b]pyridine analogues as hepatitis C virus inhibitors
-
Current treatment for hepatitis C is barely satisfactory, there is an urgent need to develop novel agents for combating hepatitis C virus infection. This study discovered a new class of thieno[2,3-b]pyridine derivatives as HCV inhibitors. First, a hit compound characterized by a thienopyridine core was identified in a cell-based screening of our privileged small molecule library. And then, structure activity relationship study of the hit compound led to the discovery of several potent compounds without obvious cytotoxicity in vitro (12c, EC50 = 3.3 μM, SI >30.3, 12b, EC50 = 3.5 μM, SI >28.6, 10l, EC50 = 3.9 μM, SI >25.6, 12o, EC 50 = 4.5 μM, SI >22.2, respectively). Although the mechanism of them had not been clearly elucidated, our preliminary optimization of this class of compounds had provided us a start point to develop new anti-HCV agents.
- Wang, Ning-Yu,Zuo, Wei-Qiong,Xu, Ying,Gao, Chao,Zeng, Xiu-Xiu,Zhang, Li-Dan,You, Xin-Yu,Peng, Cui-Ting,Shen, Yang,Yang, Sheng-Yong,Wei, Yu-Quan,Yu, Luo-Ting
-
supporting information
p. 1581 - 1588
(2014/03/21)
-
- Microwave-assisted, tetrabutylammonium hydroxide catalysed 1,4-addition of water to α,β-unsaturated ketones and α,β-ynones in aqueous solution
-
Microwave-assisted, tetrabutylammonium hydroxide catalysed 1,4-addition reactions of water to α,β-unsaturated ketones and α,β-ynones take place efficiently in water. Reactions of the resulting β-hydroxy ketones lead to the formation of either C-C bond cleavage or annulation products. This journal is
- Lee, Hyejeong,Jun, Chul-Ho
-
p. 48331 - 48335
(2014/12/11)
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- Mono- and dinucleating Ni(II), Cu(II), Zn(II) and Fe(III) complexes of symmetric and unsymmetric Schiff bases incorporating salicylimine functions - Synthetic and structural studies
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The known Schiff base, 3-(2-aminophenylamino)-1-phenylbut-2-en-1-one (1), formed by 1:1 condensation of o-phenylenediamine and benzoylacetylacetone reacts at its free amine site with salicylaldehyde and 5-tert-butylsalicylaldehyde in the presence of Ni(II) and Cu(II) acetates, or with 5-tert-butylsalicylaldehyde in the presence of Zn(II) acetate, to generate 1:1 (M:L) diimine complexes (2) of the corresponding doubly deprotonated, unsymmetric, O2N 2-tetradentate ligands. In contrast, reaction of Zn(II) acetate with 1 and salicylaldehyde led to Schiff base exchange (with loss of benzoylacetylacetone) to yield symmetric [ZnL3] [where L3 is N,N′-o-phenylenebis(salicyliminato)]. Similarly, when Fe(II) chloride was substituted for metal acetate in the reaction of 1 with 5-tert-butyl- salicylaldehyde and the initial product crystallised in the presence of dabco (as base), a related Schiff base exchange reaction occurred along with aerial oxidation of the Fe(II) to produce the neutral dinuclear [Fe III(L4)2(μ-O)] species [where L4 is N,N′-o-phenylenebis(5-tert-butylsalicyliminato)] in which Fe(III) centres are linked by an oxo group to produce two 5-coordinate Fe(III) centres; pairs of these (oxo-bridged) dinuclear complex units are further linked via elongated intermolecular Fe-Ophenolic contacts (Fe-O, 2.44 A?) to form an unusual tetranuclear supramolecular cluster. This complex was also synthesised directly by the in situ reaction of 5-tert-butyl-salicylaldehyde, o-phenylenediamine and Fe(II) chloride (2:1:1 mol ratio) in air. In an extension of these studies, the in situ reaction of the 1,3-aryl linked bis-β-diketone, 1,1-(1,3-phenylene)-bis-butane-1,3-dione), o-phenylenediamine, salicylaldehyde and Ni(II) acetate in a 1:2:2:2 ratio yielded [Ni2L5], the dinuclear analogue of the unsymmetric mononuclear Ni(II) complex 2, in which each nickel centre has a square planar environment. Reaction of the above 1,3-phenylene linked bis-β-diketone precursor with o-phenylenediamine in a 1:2 M ratio yields 1,3-bis(4-methyl-3H- benzo[b][1,4]diazepin-2-yl)benzene as its monohydrate (3·H2O) incorporating two 7-membered diaza heterocyclic rings; thus contrasting with the 'open' Schiff base structure observed for 1. X-ray structures of 1, 3·H2O, [NiL1]·py, [NiL1] ·EtOH, [NiL2], [CuL1]·py, [CuL 1]·0.5CHCl3, [(FeL4)2(μ-O) ]2·1.5THF·0.4EtOH·0.6H2O and [NiL5]·0.25EtOH·0.125py are reported.
- Meng, Qinghua,Clegg, Jack K.,Brock, Aidan J.,Jolliffe, Katrina A.,Lindoy, Leonard F.,Wei, Gang
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p. 113 - 121
(2014/04/17)
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- Highly atom-efficient oxidation of electron-deficient internal olefins to ketones using a palladium catalyst
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A 100 % atom-efficient synthesis of ketones from electron-deficient internal olefins was achieved using O2 as a "green" oxidant (see scheme, DMA=N,N-dimethylacetamide, EWG=electron-withdrawing group). Various electron-deficient olefins were oxidized to the corresponding ketones with over 99 % selectivity and without the formation of olefin isomers or their oxidized products. Copyright
- Mitsudome, Takato,Yoshida, Syuhei,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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p. 5961 - 5964
(2013/06/27)
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- Palladium-catalysed carbonylative α-arylation of acetone and acetophenones to 1,3-diketones
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Three COmponent α-arylation: A carbonylative ketone α-arylation process employing acetone for the first time, as well as acetophenones, is described (see scheme). The reaction tolerates a range of (hetero)aryl iodides and several functionalised aryl ketone coupling partners. Only low pressures of molecular CO are applied and no additional solvent is necessary. Copyright
- Schranck, Johannes,Tlili, Anis,Alsabeh, Pamela G.,Neumann, Helfried,Stradiotto, Mark,Beller, Matthias
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supporting information
p. 12624 - 12628
(2013/10/01)
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- Direct β-acyloxylation of enamines via PhIO-mediated intermolecular oxidative C-O bond formation and its application to the synthesis of oxazoles
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A direct β-acyloxylation of enamine compounds has been achieved by using iodosobenzene (PhIO) as an oxidant to realize the intermolecular oxidative C(sp2)-O bond formation between enamines and various carboxylic acids, including N-protected amino acids. The transformation tolerates a wide range of functional groups and furnishes a variety of β-acyloxy enamines that can be conveniently converted to oxazole compounds via cyclodehydration.
- Liu, Xin,Cheng, Ran,Zhao, Feifei,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
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supporting information
p. 5480 - 5483,4
(2012/12/12)
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- Direct β-acyloxylation of enamines via PhIO-mediated intermolecular oxidative C-O bond formation and its application to the synthesis of oxazoles
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A direct β-acyloxylation of enamine compounds has been achieved by using iodosobenzene (PhIO) as an oxidant to realize the intermolecular oxidative C(sp2)-O bond formation between enamines and various carboxylic acids, including N-protected amino acids. The transformation tolerates a wide range of functional groups and furnishes a variety of β-acyloxy enamines that can be conveniently converted to oxazole compounds via cyclodehydration.
- Liu, Xin,Cheng, Ran,Zhao, Feifei,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
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supporting information
p. 5480 - 5483
(2013/01/15)
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- Tandem reactions leading to benzo[c]chromen-6-ones and 3-substituted isocoumarins
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A simple and convenient protocol for the synthesis of benzo[c]chromen-6- ones and 3-substituted isocoumarins through a CuI-catalyzed tandem reaction of 2-bromobenzoates withcyclohexane-1,3-diones or acyclic 1,3-diones is developed. This strategy can also be extended to the one-pot synthesis of isoquinolin-1(2H)-one and 3,4-dihydrophenanthridine-1,6(2H,5H)-dione. A simple and convenient protocol for the synthesis of benzo[c]chromen-6-ones and 3-substituted isocoumarins through a CuI-catalyzed tandem reaction of 2-bromobenzoates with cyclohexane-1,3-dione or acyclic 1,3-dione has been developed. This strategy can also be extended to the one-pot synthesis of isoquionlin-1(2H)-one and 3,4-dihydrophenanthridine-1,6-(2H,5H)-dione. Copyright
- Fan, Xuesen,He, Yan,Cui, Liangyan,Guo, Shenghai,Wang, Jianji,Zhang, Xinying
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supporting information; experimental part
p. 673 - 677
(2012/03/10)
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- Discovery of phenylaminopyridine derivatives as novel HIV-1 non-nucleoside reverse transcriptase inhibitors
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We identified a novel class of aryl-substituted triazine compounds as potent non-nucleoside reverse transcriptase inhibitors (NNRTIs) during a high-throughput screening campaign that evaluated more than 200000 compounds for antihuman immunodeficiency virus (HIV) activity using a cell-based full replication assay. Herein, we disclose the optimization of the antiviral activity in a cell-based assay system leading to the discovery of compound 27, which possessed excellent potency against wild-type HIV-1 (EC50 = 0.2 nM) as well as viruses bearing Y181C and K103N resistance mutations in the reverse transcriptase gene. The X-ray crystal structure of compound 27 complexed with wild-type reverse transcriptase confirmed the mode of action of this novel class of NNRTIs. Introduction of a chloro functional group in the pyrazole moiety dramatically improved hERG and CYP inhibition profiles, yielding highly promising leads for further development.
- Kim, Junwon,Park, Changmin,So, Wonyoung,Jo, Mina,Ok, Taedong,Kwon, Jeongjin,Jo, Suyeon,Choi, Jihyun,Kim, Hyoung Cheul,Lee, Doohyun,Kim, Youngmi,Ko, Yoonae,Choi, Inhee,Kong, Sunju,Park, Youngsam,Yoon, Jaewan,Ju, Moon Kyeong,Kim, Junghwan,Han, Sung-Jun,Kim, Tae-Hee,Cechetto, Jonathan,Nam, Jiyoun,Sommer, Peter,Liuzzi, Michel,Lee, Jinhwa,No, Zaesung
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supporting information
p. 678 - 682,5
(2020/08/31)
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- Regioselectivity switch: Gold(I)-catalyzed oxidative rearrangement of propargyl alcohols to 1,3-diketones
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The gold(I)-catalyzed oxidative rearrangement of propargyl alcohols provides an efficient and selective route to 1,3-diketones under mild conditions. Pyridine-N-oxides were used as external oxidants with, different from related substrates, no alkylidenecycloalkanones or oxetan-3-ones formed as side-products.
- Hashmi, A. Stephen K.,Wang, Tao,Shi, Shuai,Rudolph, Matthias
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p. 7761 - 7767
(2012/11/07)
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- Enantioselective synthesis of optically pure β-amino ketones and γ-aryl amines by Rh-catalyzed asymmetric hydrogenation
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A series of optically pure β-amino ketones have been synthesized in high enantioselectivities (ee > 99%) by Rh-DuanPhos-catalyzed asymmetric hydrogenation of readily prepared β-keto enamides. Further reduction of these β-amino ketones with hydrogen and Pd/C leads to the formation of a variety of protected enantiomerically pure γ-aryl amines (ee > 99%), which are key building blocks in many bioactive molecules.
- Geng, Huiling,Huang, Kexuan,Sun, Tian,Li, Wei,Zhang, Xiaowei,Zhou, Le,Wu, Wenjun,Zhang, Xumu
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supporting information; experimental part
p. 332 - 334
(2011/03/19)
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- Electron-deficient aryl β-diketones: Synthesis and novel tautomeric preferences
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Fluorinated aryl β-diketones were prepared using Claisen and electrophilic fluorination methods. The keto-enol and enol-enol tautomerism of these compounds were examined in the solid state, as neat liquids and in polar, aprotic solution by crystallography and spectroscopy. Neat-liquid spectroscopic measurements as well as single crystal X-ray crystallographic results for selected electron-deficient aryl β-diketones suggest a single, chelated cis-enol isomer that is conjugated with the aryl ring. In polar aprotic solvents, nonfluorinated aryl β-diketones equilibrate rapidly from the chelated cis-enol form to a tautomeric mixture of cis-chelated enol and a substantial proportion of the diketone form, trifluoromethylated aryl β-diketones show only limited equilibration from the chelated cis-enol to the diketone form, with 2-fluoro-1-aryl β-diketones again displaying only the diketonic form.
- Sloop, Joseph C.,Boyle, Paul D.,Fountain, Augustus W.,Pearman, William F.,Swann, Jacob A.
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experimental part
p. 936 - 941
(2011/04/17)
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- Albumin-directed stereoselective reduction of 1,3-diketones and β-hydroxyketones to anti diols
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The reduction of 1,3-diketones and β-hydroxyketones with NaBH 4 in aqueous acetonitrile is highly stereoselective in the presence of stoichiometric amounts of bovine or human albumin, giving anti 1,3-diols with d.e. up to 96%. The same reaction, without albumin, gives syn and anti 1,3-diols in approximately 1:1 ratio. The presence of an aromatic carbonyl group is essential for diastereoselectivity in the NaBH4/albumin reduction of both 1,3-diketones and β-hydroxyketones. Thus, 3-hydroxy-1-(p-tolyl)-1- butanone is stereoselectively reduced in the presence of albumin, while reduction of its isomer 4-(p-tolyl)-4-hydroxy-2-butanone is not stereoselective. The albumin-controlled reduction is not stereospecific as both enantiomers of 1-aryl-3-hydroxy-1-butanones are reduced to diols with identical stereoselectivities. Circular dichroism of the bound substrates confirms that aromatic ketones are recognized by the protein's IIA binding site. Binding studies also suggest that 1,3-diketones are recognized in their enol form. From the effect of pH on binding of a diketone it is concluded that, in the complex with the substrate, ionizable residues His242 and Lys199 are in the neutral and protonated forms, respectively. A homology model of BSA was obtained and docking of model substrates confirms the preference of the protein for aromatic ketones. Modelling of the complexes with the substrates also allows us to propose a mechanism for the reduction of 1,3-diketones in which the chemoselective reduction of the first (aliphatic) carbonyl is followed by the diastereoselective reduction of the second (aromatic) carbonyl. The role of albumin is thus a combination of chemo- and stereocontrol.
- Berti, Federico,Bincoletto, Simone,Donati, Ivan,Fontanive, Giampaolo,Fregonese, Massimo,Benedetti, Fabio
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experimental part
p. 1987 - 1999
(2011/04/25)
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- High-yielding oxidation of β-hydroxyketones to β-diketones using o-Iodoxybenzoic acid
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The oxidation of β-hydroxyketones to β-diketones was systematically investigated. o-Iodoxybenzoic acid (IBX) was found to be efficient, operationally easy, and superior to other common oxidants. The reaction is suitable for milligram- to gram-scale oxidations.
- Bartlett, Samuel L.,Beaudry, Christopher M.
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experimental part
p. 9852 - 9855
(2012/01/02)
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- Tandem reaction of 1,2-allenic ketone with α-halo ketone or α-halo ester in water: An efficient and sustainable synthesis of 1,3,4′-tricarbonyl compounds
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An efficient and sustainable synthesis of the otherwise difficult to obtain 1,3,4′-tricarbonyl compounds through a water mediated, TBAF·3H2O promoted unprecedented tandem reaction of 1,2-allenic ketone with α-halo ketone or α-halo ester has been developed. Remarkably enhanced reactivity and improved chemoselectivity by using water as the reaction medium was observed. The 1,3,4′-tricarbonyl compounds facilitate further versatile transformations, which underscores the importance of these products as synthetic intermediates. The Royal Society of Chemistry.
- Fan, Xuesen,He, Yan,Cui, Liangyan,Zhang, Xinying,Wang, Jianji
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supporting information; experimental part
p. 3218 - 3223
(2011/12/16)
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- A tandem reaction of organozinc reagent prepared from palladium-catalyzed umpolung method: Diastereoselective formation of cyclohexene derivatives bearing three adjacent stereocenters
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In the presence of a palladium catalyst, treatment of γ-acyloxy- α,β-unsaturated ketone with bis(iodozincio)methane caused umpolung of π-allylpalladium to give a zinc dienolate. Thus formed zinc species afforded a cyclohexene derivative via a self-condesation reaction. It is noteworthy that the three adjacent stereogenic centers were created in a single process with quite high diastereoselectivity. The Royal Society of Chemistry 2011.
- Sada, Mutsumi,Nomura, Kenichi,Matsubara, Seijiro
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experimental part
p. 1389 - 1393
(2011/04/16)
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- 1,4-Addition of Bis(iodozincio)methane to α,β-Unsaturated ketones: Chemical and theoretical/computational studies
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1,4-Addition of bis(iodozincio)methane to simple α,β-unsaturated ketones does not proceed well; the reaction is slightly endothermic according to DFT calculations. In the presence of chlorotrimethylsilane, the reaction proceeded efficiently to afford a silyl enol ether of β-zinciomethyl ketone. The CZn bond of the silyl enol ether could be used in a cross-coupling reaction to form another C-C bond in a one-pot reaction. In contrast, 1,4-addition of the dizinc reagent to enones carrying an acyloxy group proceeded very efficiently without any additive. In this case, the product was a 1,3-diketone, which was generated in a novel tandem reaction. A theoretical/computational study indicates that the whole reaction pathway is exothermic, and that two zinc atoms of bis(iodozincio)methane accelerate each step cooperatively as effective Lewis acids.
- Sada, Mutsumi,Furayama, Taniyuki,Komagawa, Shinsuke,Uchiyama, Masanobu,Matsubara, Seijiro
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experimental part
p. 10474 - 10481
(2010/10/21)
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- Te-1-acylmethyl and Te-1-iminoalkyl telluroesters: Synthesis and thermolysis leading to 1,3-diketones and O-alkenyl and O-imino esters
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A series of Te-1-acylmethyl carbotelluroates was prepared in good isolated yields from the reaction of potassium carbotelluroates with -haloketones in acetonitrile. Thermolysis of the telluroesters afforded vinyl esters in 20-50% yields, while treatment of the carbotellurorates with potassium t-butanolate led to 1,3-diketones in 30-75% yields with the liberation of black tellurium. The reaction of potassium carbotelluroates with -haloaceto oximes gave O-acyl oximes in 50-70% yields via Te-1-iminomethylcarbotelluroates. Copyright Taylor & Francis Group.
- Nakaiida, Shoho,Kato, Shinzi,Niyomura, Osamu,Ishida, Masaru,Ando, Fumio,Koketsu, Jugo
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experimental part
p. 930 - 946
(2010/08/04)
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- Cobalt-catalyzed generation of 1,4-dienes as synthons for 1,3-dicarbonyl compounds and their application in natural product syntheses
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The cobalt-catalyzed 1,4-hydrovinylation of alkenes with 1,3-dienes and the cobalt-catalyzed Diels-Alder reaction of alkynes with 1,3-dienes lead to acyclic and cyclic 1,4-dienes, respectively. These products can be transformed into 1,3-dicarbonyl functional groups by ozonolysis or alternative carbon-carbon double bond cleaving reactions. The application towards the synthesis of hepialone and a pyranone-type lipid from Vanilla beans is described. Georg Thieme Verlag Stuttgart · New York.
- Hilt, Gerhard,Arndt, Marion,Weske, Damian F.
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experimental part
p. 1321 - 1324
(2010/07/02)
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- Highly efficient indium(III)-mediated cyclisation of 5-hydroxy-1,3- diketones to 2,3-dihydro-4H-pyran-4-ones; Mechanistic insights from in situ Fourier transform infrared spectroscopy
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5-Hydroxy-1,3-diketones have been synthesised in a facile one-pot reaction from the treatment of acid chlorides with non-substituted ketones and LiHMDS. Subsequent cyclisation to 2,3-dihydro-4H-pyran-4-ones occurs rapidly and in high yield (89-99%) when mediated by anhydrous indium(iii) chloride. A spectroscopic study of the reaction using in situ Fourier transform infrared (FTIR) spectroscopy has shown the reaction to be highly dependent on temperature, metal complex formation and InCl3 concentration. Since the reaction is deactivated by the precipitation of [InCl3·(H 2O)3], the concurrent use of a stronger drying agent, such as molecular sieves 4 A or anhydrous MgSO4, allows the reaction to be successfully carried out at relatively low loadings of InCl 3 (1-10%). In their absence, the optimum reaction conditions were found to be a diketone:InCl3 ratio of 3:1 in toluene, and a reaction temperature of 80 °C.
- Andrews, Philip C.,Gee, William J.,Junk, Peter C.,Krautscheid, Harald
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supporting information; experimental part
p. 698 - 705
(2010/05/11)
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