- Solid polymer substrates and coated fibers containing 2,4,6-trinitrobenzene motifs as smart labels for the visual detection of biogenic amine vapors
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Attempts to polymerize trinitrobenzene derivatives (TNB) have been fruitless so far. Accordingly, polymers containing TNB have not been exploited in spite of their envisaged potential applications. Here, we describe two ways for preparing polymers with TNB moieties thus overcoming the previously reported polymerization impairments. We also report on the exploitation of the materials, both obtained as tractable transparent films and coated fibers, as smart labels for the visual detection of amine vapors. More precisely, amines in the atmosphere surrounding the sensory materials diffuse into them reacting with the TNB motifs forming highly colored Meisenheimer complexes, giving rise to development of color and to the naked eye sensing phenomenon. This is the case of highly volatile amines, such as trimethylamine, produced in food spoilage, specifically in the deterioration of fish or meat, for which the color development of the smart labels can be used as a visual test for food freshness.
- Pablos, Jesús L.,Vallejos, Saúl,Mu?oz, Asunci?n,Rojo, María J.,Serna, Felipe,García, Félix C.,García, José M.
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Read Online
- In vivo and in vitro effects of methacrylanilides and acetylcarboxanilide on alkaline phosphatase activity of Echinococcus multilocularis metacestodes
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In our search for effective chemotherapy of alveolar hydatid disease we are investigating key enzymes of Echinococcus multilocularis metacestodes.Isatin (2,3-indolinedione) is well known as an inhibitor of alkaline phosphatase activity, and has been previously investigated.Acetylcarboxanilide, an "open drug" of isatin and 2 methacrylanilides were evaluated for their ability to inhibit alkaline phosphatase activity of Echinococcus multilocularis metacestodes in vivo.These "open drugs" are more efficient than isatin, and para-chloromethacrylanilide exhibits a strongselectivity for the parasite enzyme and is also effective in vitro.The results obtained with para-chloromethacrylanilide are promising.Echinococcus multilocularis / alkaline phosphatase / synthetic inhibitors /anilides
- Audin, P,Sarciron, ME,Paris, J,Petavy, AF
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- Efficient synthesis of aromatic sec-amides from esters: Synthetic utility of bislithium amides
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Convenient, efficient preparation of aromatic sec-amides from esters has been accomplished using dilithium amides which are easily prepared by treatment of aromatic amines with 2 equiv of BuLi in THF. This new method allows a facile formation of amide bond even with sterically hindered esters.
- Ooi, Takashi,Tayama, Eiji,Yamada, Masao,Maruoka, Keiji
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Read Online
- Silver-Promoted Fluorination Reactions of α-Bromoamides
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Silver-promoted C?F bond formation in α-bromoamides by using AgF under mild conditions is reported. This simple method enables access to tertiary, secondary, and primary alkyl fluorides involving biomolecular scaffolds. This transformation is applicable to primary and secondary amides and shows broad functional-group tolerance. Kinetics experiments revealed that the reaction rate increased in the order of 3°>2°>1° α-carbon atom. In addition, it was found that the acidic amide proton plays an important role in accelerating the reaction. Mechanistic studies suggested generation of an aziridinone intermediate that undergoes subsequent nucleophilic addition to form the C?F bond with stereospecificity (i.e., retention of configuration). The synthesis of sterically hindered alcohols and ethers by using AgI is also demonstrated. Examples of reactions of α-bromoamides with O nucleophiles are presented.
- Mizuta, Satoshi,Kitamura, Kanami,Kitagawa, Ayako,Yamaguchi, Tomoko,Ishikawa, Takeshi
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p. 5930 - 5935
(2021/02/01)
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- Electrochemical reduction of fluoroalkyl sulfones for radical fluoroalkylation of alkenes
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Radical fluoroalkylation of alkenes has been developed by electrochemical reduction of fluoroalkyl sulfones. A series of electron-deficient alkenes readily undergo hydrofluoroalkylation in good to excellent yields. This chemistry represents the first example of electrochemical generation of fluoroalkyl radicals from sulfones, which are used for practical radical fluoroalkylation of organic compounds.
- Deng, Ling,Hu, Jinbo,Ni, Chuanfa,Zhou, Xin
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supporting information
p. 8750 - 8753
(2021/09/08)
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- A benzene-bridged divanadium complex-early transition metal catalyst for alkene alkylarylation with PhI(O2CR)2viadecarboxylation
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The synthesis, structure and catalytic activity of a benzene-bridged divanadium complex were comprehensively studied. The reduction of (Nacnac)VCl2(1) (Nacnac = (2,6-iPr2C6H3NCMe)2HC) supported by β-diketiminate with potassium graphite (KC8) by employing benzene as the solvent allows access to the benzene-bridged inverted-sandwich divanadium complex (μ-η6:η6-C6H6)[V(Nacnac)]2(2a), which can catalyze alkene alkylarylation with hypervalent iodine(iii) reagents (HIRs)viadecarboxylation to generate regioselectively diverse indolinones. Furthermore, the mild nature of this reaction was amenable to a wide range of functionalities on alkenes and HIRs. Mechanistic studies revealed a relay sequence of decarboxylative radical alkylation/radical arylation/oxidative re-aromatization.
- Zhang, Lei,Zhou, Hongfei,Bai, Shaokun,Li, Shaodan
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supporting information
p. 3201 - 3206
(2021/03/16)
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- Bromo Radical-Mediated Photoredox Aldehyde Decarbonylation towards Transition-Metal-Free Hydroalkylation of Acrylamides at Room Temperature
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Herein, we report a visible-light-mediated hydroalkylation reaction of alkenes using easily available aldehydes as alkyl sources via bromo radical-promoted photoredox decarbonylation. This protocol provides an alternative entry to C(sp3)?C(sp3) bond formation and features considerable advantages including mild and clean reaction conditions, obviation for transition-metal catalyst, and good functional group compatibility.
- Deng, Guo-Jun,Huang, Huawen,Sun, Zhaozhao,Wang, Qiaolin
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supporting information
(2021/12/03)
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- Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals
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A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α-halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo-coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal-based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α-carbonyl bromides were explored with broad substrate scopes.
- Das, Sanju,De Sarkar, Suman,Mandal, Tanumoy
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supporting information
(2021/12/10)
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- Chemistry of Tertiary Carbon Center in the Formation of Congested C?O Ether Bonds
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Nucleophilic substitutions, including SN1 and SN2, are classical and reliable reactions, but a serious drawback is their intolerance for both bulky nucleophiles and chiral tertiary alkyl electrophiles for the synthesis of a chiral quaternary carbon center. An SRN1 reaction via a radical species is another conventional method used to carry out substitution reactions of bulky nucleophiles and alkyl halides, but chiral tertiary alkyl electrophiles cannot be used. Therefore, a stereospecific nucleophilic substitution reaction using chiral tertiary alkyl electrophiles and bulky nucleophiles has not yet been well studied. In this paper, we describe the reaction of tertiary alkyl alcohols and non-chiral or chiral α-bromocarboxamides as a tertiary alkyl source for the formation of congested ether compounds possessing two different tertiary alkyl groups on the oxygen atom with stereoretention.
- Hirata, Goki,Takeuchi, Kentarou,Shimoharai, Yusuke,Sumimoto, Michinori,Kaizawa, Hazuki,Nokami, Toshiki,Koike, Takashi,Abe, Manabu,Shirakawa, Eiji,Nishikata, Takashi
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supporting information
p. 4329 - 4334
(2020/12/23)
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- Polysubstituted tryptamine benzamide compound and preparation method and application thereof
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The invention discloses a polysubstituted tryptamine benzamide compound and a preparation method and application thereof. The compound is characterized in that the compound is a polysubstituted tryptamine benzamide compound with a structural formula shown as a formula I or a pharmaceutically acceptable salt, ester or solvate of the polysubstituted tryptamine benzamide compound with the structuralformula shown as the formula I. The preparation method comprises the following steps: (1) carrying out amide synthesis reaction on a compound shown in a formula II and a compound shown in a formula III to obtain a compound shown in a formula IV; and (2) reacting the compound as shown in the formula IV with V to carry out Michael addition reaction so as to obtain a compound as shown in the formulaI. The polysubstituted tryptamine benzamide compound and a preparation method and application thereof have the advantages that tumor growth can be effectively inhibited, so that growth stagnation, differentiation or apoptosis of tumor cells is induced, and the effect of inhibiting tumor cell proliferation is achieved.
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Paragraph 0038
(2020/05/30)
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- Copper-Catalyzed Radical N-Demethylation of Amides Using N-Fluorobenzenesulfonimide as an Oxidant
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An unprecedented N-demethylation of N-methyl amides has been developed by use of N-fluorobenzenesulfonimide as an oxidant with the aid of a copper catalyst. The conversion of amides to carbinolamines involves successive single-electron transfer, hydrogen-atom transfer, and hydrolysis, and is accompanied by formation of N-(phenylsulfonyl)benzenesulfonamide. Carbinolamines spontaneously decompose to N-demethylated amides and formaldehyde, because of their inherent instability.
- Yi, Xuewen,Yi, Xuewen,Lei, Siyu,Liu, Wangsheng,Che, Fengrui,Yu, Chunzheng,Liu, Xuesong,Wang, Zonghua,Zhou, Xin,Zhang, Yuexia
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supporting information
p. 4583 - 4587
(2020/05/05)
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- Stereospecific Electrophilic Fluorocyclization of α,β-Unsaturated Amides with Selectfluor
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An efficient fluorocyclization of α,β-unsaturated amides through a formal halocyclization process is developed. The reaction proceeds under transition-metal-free conditions and leads to the formation of fluorinated oxazolidine-2,4-diones with excellent regio- and diastereoselectivity. The evaluation of the reaction mechanism based on preliminary experiments and density functional theory calculations suggests that a synergetic syn-oxo-fluorination occurs and is followed by an anti-oxo substitution reaction. The reaction opens a new window in the field of stereospecific fluorofunctionalization.
- Fei, Haiyang,Fu, Yao,Jalani, Hitesh B.,Li, Guigen,Lu, Hongjian,Wu, Hongmiao,Xu, Zheyuan,Zhu, Lin
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supporting information
(2020/03/30)
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- Nontraditional Application of the Photo-Fenton Process: A Novel Strategy for Molecular Construction Using Formamide and Flow Chemistry
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Instead of destroying organic compounds, for the first time the photo-Fenton reaction was employed to construct them. Oxindole and spiro-oxindole scaffolds, which are frequently found in natural products, were selected as molecular targets. The development of a photochemical flow reactor employing the photo-Fenton reaction in formamide resulted in an excellent synthetic methodology for oxindoles. Non-anhydrous conditions are required, and readily available chemicals and mild conditions are employed. Also, novel synthetic approaches for new spiro compounds were efficiently developed using functionalized oxindoles as key intermediates.
- Andrade, Leandro H.,Correia, Valquíria G.,Hornink, Milene M.,Sanabria, Marialy N.
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supporting information
p. 2288 - 2297
(2020/11/23)
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- N-demethylation method for amide and application thereof
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The invention discloses an N-demethylation method for amide and application thereof. The method comprises the following steps: heating raw amide to 40-120 DEG C under the action of N-fluorodibenzenesulfonamide and a bivalent copper salt, and carrying out a reaction to obtain demethylated amide. The chemical structural formula of the raw amide is described in the specification; the chemical structural formula of the demethylated amide is described in the specification; and in the formulas, R1 is selected from aryl, alkyl and alkenyl groups, and R2 is selected from aryl, alkyl and alkenyl groups. With the method, N-demethylation of amide can be achieved; and the method has the advantages of mild reaction conditions, easiness in operation, low cost and the like.
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Paragraph 0034-0065; 0142
(2020/06/30)
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- Copper-Catalyzed Tertiary Alkylative Cyanation for the Synthesis of Cyanated Peptide Building Blocks
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In this paper, we report efficient cyanation of various peptides containing the α-bromocarbonyl moiety using a Cu-catalyzed radical-based methodology employing zinc cyanide as the cyanide source. Mechanistic studies revealed that in situ formed CuCN was a key intermediate during the catalytic cycle. Our method could be useful for the synthesis of modified peptides containing quaternary carbons.
- Miwa, Naoki,Tanaka, Chihiro,Ishida, Syo,Hirata, Goki,Song, Jizhou,Torigoe, Takeru,Kuninobu, Yoichiro,Nishikata, Takashi
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supporting information
p. 1692 - 1697
(2020/02/04)
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- Hypervalent Iodine Mediated Oxidative Cyclization of Acrylamide N-Carbamates to 5,5-Disubstituted Oxazolidine-2,4-diones
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A metal-free oxidative cyclization of N-Boc-acrylamides with (diacetoxyiodo)benzene in acetic acid produced 5,5-disubstituted oxazolidine-2,4-diones with the formation of a C-O bond in moderate to excellent yields. In addition, the reaction was diastereospecific with N-Boc-2,3-dimethylacrylamides and proceeded with phenyl migration in the case of an N-Boc-2-phenylacrylamide to generate a 5-acetoxy-5-benzyloxazolidine-2,4-dione.
- Duddupudi, Anantha Lakshmi,Pandey, Pankaj,Vo, Hien,Welsh, Colin L.,Doerksen, Robert J.,Cuny, Gregory D.
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p. 7549 - 7557
(2020/06/03)
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- Systematic Study of the Glutathione Reactivity of N-Phenylacrylamides: 2. Effects of Acrylamide Substitution
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A comprehensive understanding of structure-reactivity relationships is critical to the design and optimization of cysteine-targeted covalent inhibitors. Herein, we report glutathione (GSH) reaction rates for N-phenyl acrylamides with varied substitutions at the α- and β-positions of the acrylamide moiety. We find that the GSH reaction rates can generally be understood in terms of the electron donating or withdrawing ability of the substituent. When installed at the β-position, aminomethyl substituents with amine pKa's > 7 accelerate, while those with pKa's 7 slow the rate of GSH addition at pH 7.4, relative to a hydrogen substituent. Although a computational model was able to only approximately capture experimental reactivity trends, our calculations do not support a frequently invoked mechanism of concerted amine/thiol proton transfer and C-S bond formation and instead suggest that protonated aminomethyl functions as an electron-withdrawing group to reduce the barrier for thiolate addition to the acrylamide.
- Birkholz, Adam,Kopecky, David J.,Volak, Laurie P.,Bartberger, Michael D.,Chen, Yuping,Tegley, Christopher M.,Arvedson, Tara,McCarter, John D.,Fotsch, Christopher,Cee, Victor J.
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p. 11602 - 11614
(2020/12/04)
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- Visible Light-Induced Difunctionalization of Alkynes: The Synthesis of Thiazoles and 1,1-Dibromo-1-en-3-ynes
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A visible light-induced cascade cyclization of thioamides with alkynes was developed to synthesize 1,3-thiozoles. The sulfur radical generated from thioamide via the single-electron transfer (SET) pathway was promoted by photocatalysis as a key intermediate in this reaction. When bromoalkynes were used as the substrate, the self-coupling products 1,1-dibromo-1-en-3-ynes were obtained in moderate yields, and an energy transfer pathway for this transformation promoted by visible-light photocatalysis was proposed.
- Huang, Xiaoying,Chen, Hui,Huang, Zhongzhi,Xu, Yanli,Li, Fangyao,Ma, Xianli,Chen, Yanyan
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p. 15283 - 15293
(2019/12/04)
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- Regioselective Acetoxylation of Terminal Olefins Using a Palladium(II)–Thiadiazole Catalyst
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First-time use of a palladium(II)–thiadiazole catalyst in the allylic oxidation of terminal olefins to linear allylic acetates. Employing this strategy, a range of allylic esters (20 examples) were synthesized in 43 % to 80 % yield with excellent regio- and stereoselectivities.
- Li, Xiaohan,Sun, Bin,Zhou, Jiadi,Jin, Can,Yu, Chuangming
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supporting information
p. 2635 - 2638
(2019/04/04)
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- The Allylic Acetoxylation of 1,1-Disubstituted Alkenes Catalyzed by a Palladium(II)/Monothiadiazole Ligand System
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A palladium(II)/monothiadiazole ligand catalytic system and its application in catalyzing the acetoxylation of 1,1-disubstituted alkenes have been developed. With this newly designed monothiadiazole thioether ligand, the reaction showed a broad scope with respect to 1,1-disubstituted olefins, giving the corresponding products in yields of 30-86percent.
- Jin, Can,Li, Xiaohan,Sun, Bin,Wang, Jiayang,Yang, Jin,Yu, Chuangming,Zhang, Xun,Zhuang, Xiaohui
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supporting information
p. 1479 - 1483
(2019/07/15)
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- Synthesis of Perfluoroalkyl-Substituted Oxindoles through Organophotoredox-Catalyzed Perfluoroalkylation of N-arylacrylamides with Perfluoroalkyl Iodides
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An efficient process was developed for the perfluoroalkylation of N -arylacrylamides through an organocatalyzed photoredox/cyclization reaction of N -arylacrylamides with inexpensive perfluoroalkyl iodide reagents. The reaction employs an inexpensive organic dye, eosin Y, as the photoredox catalyst and is run under irradiation by a 26 W LED lightbulb.
- Yang, Zhiyong,Tang, Anjiang
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supporting information
p. 1061 - 1066
(2019/05/24)
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- Catalyst-free and selective trifluoromethylative cyclization of acryloanilides using PhICF3Cl
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Trifluoromethylation-triggered cyclization of alkenes provides a useful route to CF3-containing cyclic compounds. Current approaches to generate CF3-based initiators from a CF3 source require a catalyst or an activator. This work describes a catalyst-free protocol to innately produce electrophilic CF3 species from PhICF3Cl for trifluoromethylative cyclization of acryloanilides. A new domino biscyclization of dienes has been developed leading to trifluoroethylated tetrahydroindenoquinolinones with chemo- and stereo-selectivity.
- Guo, Jia,Xu, Cong,Wang, Ling,Huang, Wanqiao,Wang, Mang
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supporting information
p. 4593 - 4599
(2019/05/17)
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- Dehydrogenative Silylation of Alkenes for the Synthesis of Substituted Allylsilanes by Photoredox, Hydrogen-Atom Transfer, and Cobalt Catalysis
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A synergistic catalytic method combining photoredox catalysis, hydrogen-atom transfer, and proton-reduction catalysis for the dehydrogenative silylation of alkenes was developed. With this approach, a highly concise route to substituted allylsilanes has been achieved under very mild reaction conditions without using oxidants. This transformation features good to excellent yields, operational simplicity, and high atom economy. Based on control experiments, a possible reaction mechanism is proposed.
- Yu, Wan-Lei,Luo, Yong-Chun,Yan, Lei,Liu, Dan,Wang, Zhu-Yin,Xu, Peng-Fei
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supporting information
p. 10941 - 10945
(2019/07/17)
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- Nickel-Catalyzed Transformation of Diazoacetates to Alkyl Radicals Using Alcohol as a Hydrogen Source
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A nickel-catalyzed transformation of diazoacetates to α-carbonyl methylene radicals has been disclosed in the presence of hyperoxide using ethanol as a hydrogen source and solvent. This strategy is successfully applied in the formation of indolin-2-ones or 1,4-dicarbonyl compounds from acrylamides or enamides in moderate to good yields. These reactions undergo radical addition onto C-C double bonds followed by a cyclization/oxidation or an oxidation/hydrolysis process, respectively.
- Zhao, Jingjing,Li, Pan,Xu, Yaohua,Shi, Yixin,Li, Fuwei
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supporting information
p. 9386 - 9390
(2019/11/28)
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- Conjugate addition from the excited state
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Conjugate addition occurs efficiently from excited hydrazide based acrylanilides under both UV and metal free visible light irradiations. The reaction proceeds via an excited state encounter complex that bifurcates either via an electron or energy transfer pathway. The generality of excited state conjugate addition is demonstrated using chloromethylation and by thiol addition.
- Iyer, Akila,Ahuja, Sapna,Jockusch, Steffen,Ugrinov, Angel,Sivaguru, Jayaraman
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supporting information
p. 11021 - 11024
(2018/10/08)
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- Synthesis of oxindoles via Cu-mediated reactions between N-phenylacrylamides and ethyl 2-bromo-2-methylpropionate
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A novel way of synthesizing alkylated oxindoles via Cu-mediated atom transfer radical addition reaction between N-phenylacrylamides and ethyl 2-bromo-2-methylpropionate has been described. It was found that the use of N,N,N′,N′-1,1,2,2,-tetramethylethylenediamine as ligand was important for achieving good yields. Additionally, the use of DMSO as solvent and running the reaction at 130 °C were also crucial. In some cases, the product can be further brominated when the reaction temperature was raised to 150 °C.
- Liu, Da,Zhuang, Shaobo,Chen, Xiang,Yu, Lin,Yu, Yongqi,Hu, Liang,Tan, Ze
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supporting information
p. 612 - 616
(2018/01/18)
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- Iron-Catalyzed Synthesis of Oxindoles: Application to the Preparation of Pyrroloindolines
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A novel and highly efficient synthetic approach to pyrroloindolines has been developed. The process is based on tandem radical addition/cyclization with inexpensive iron catalyst. This method tolerates a wide range of N-methyl-N-arylacrylamides as well carbamoyl radicals, providing access to a variety of functionalized 3,3-disubstituted oxindoles, key intermediates for many bioactive pyrroloindolines such as (±)-esermethole, (±)-deoxyeseroline, and (±)-physovenol methyl ether.
- Correia, Valquírio G.,Abreu, Juliana C.,Barata, Caio A. E.,Andrade, Leandro H.
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supporting information
p. 1060 - 1063
(2017/03/15)
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- Substituted oxoindole-benzimidazolium salt compound and preparation method thereof
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The invention discloses a series of substituted oxoindole-benzimidazolium salt compounds with the structural general formula (shown as I) and a preparation method thereof. The target compound is obtained by carrying out six steps of acylation, methylation, iodo-annulation, inoculation of benzimidazole, coupling and salting on aniline serving as a raw material. An in-vitro anti-tumor activity cell toxicity test result shows that some of the compounds are relatively high in cytotoxic activity.
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Paragraph 0005; 0009; 0010
(2017/05/03)
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- Combining Eosin y with Selectfluor: A Regioselective Brominating System for Para-Bromination of Aniline Derivatives
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A mild, metal-free, and absolutely para-selective bromination of aniline derivatives has been developed in excellent yields, wherein the organic dye Eosin Y is employed as the bromine source in company with Selectfluor. Neither air nor moisture sensitive, this facile reaction proceeds smoothly at room temperature and completes within a short time. Mechanistic studies indicate a radical pathway; therefore, the existence of an in situ generated brominating reagent, "Selectbrom", is postulated, which may reasonably account for the unique regioselectivity for the para-bromination of N-acyl- as well as N-sulfonylanilines.
- Huang, Binbin,Zhao, Yating,Yang, Chao,Gao, Yuan,Xia, Wujiong
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supporting information
p. 3799 - 3802
(2017/07/26)
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- Visible light sensitization of benzoyl azides: Cascade cyclization toward oxindoles: Via a non-nitrene pathway
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Visible light sensitization of benzoyl azides was examined in reaction with N-phenylmethacrylamides to afford biologically important oxindoles and spirooxindoles via a cascade cyclization under mild reaction conditions. Mechanistic studies suggested a non-nitrene pathway, where triplet benzoyl azides act as the reactive intermediate.
- Bagal, Dattatraya B.,Park, Sung-Woo,Song, Hyun-Ji,Chang, Sukbok
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supporting information
p. 8798 - 8801
(2017/08/09)
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- ECO-FRIENDLY MATERIALS AND METHODS FOR RENEWABLE AND SUSTAINABLE APPLICATIONS IN MATERIAL CHEMISTRY
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The invention relates to novel hydrazide-based templates, methods of making the same, and methods of using the hydrazide-based templates as molecular scaffolds for asymmetric light driven transformations, light driven material synthesis, and biological applications. Furthermore, the present invention relates to photoinitiators, monomers, and polymers derived from biomass, together with methods and methods of using the same.
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- Silver-Catalyzed Decarboxylative Radical Addition/Cyclization of α,α-Difluoroarylacetic Acids with Acrylamides To Synthesize Difluorinated Oxindoles
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A facile silver-catalyzed decarboxylative radical addition/cyclization reaction of α,α-difluoroarylacetic acids and acrylamides has been disclosed. The method provides a highly attractive approach to synthesize a series of difluorinated oxindoles that contain various functional groups in moderate to good yields under mild conditions. Moreover, experimental studies reveal that the CF2 group of the α,α-difluoroarylacetic acids plays a vital role in the transformation.
- Li, Yin-Long,Wang, Ji-Bo,Wang, Xue-Lin,Cao, Yang,Deng, Jun
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supporting information
p. 6052 - 6059
(2017/11/14)
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- 3 - (2, 2 - Dimethyl) c cyano - 3 - alkyl (aryl) based indolone and its preparation method
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3-(2,2-dimethyl) propionitrile-3-alkyl (aryl) indolone with a following formula is prepared by a series addition / C-H cyclization reaction of reaction substrates of N-aryl acrylamide with a formula B and azodiisobutyronitrile (AIBN) in a reaction solution in the presence of a catalyst copper halide (such as copper iodide or bromide copper) and an oxidation agent of organic peroxide (such as di-tert-butyl peroxide).
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Paragraph 0030-0034
(2018/04/01)
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- Mechanistic Insights into Temperature-Dependent Trithiocarbonate Chain-End Degradation during the RAFT Polymerization of N-Arylmethacrylamides
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Mechanistic insights into trithiocarbonate degradation during the RAFT polymerization of N-arylmethacrylamides are reported. Previous work by our group showed significant RAFT agent degradation during the polymerization of N-arylmethacryloyl sulfonamides at 70 °C. Herein we report the influence of methacrylamide structure on trithiocarbonate degradation during the RAFT polymerizations of N-phenylmethacrylamide (PhMA) and N-benzylmethacrylamide (BnMA) in DMF at 70 and 30 °C. UV-vis spectroscopy revealed trithiocarbonate degradation occurs exclusively after covalent addition of monomer to the RAFT agent, with 60% trithiocarbonate degradation occurring after 12 h during the polymerization of PhMA at 70 °C compared to only 3% degradation measured during the polymerization of BnMA under identical conditions. Small molecule analogues of trithiocarbonate-functional poly(PhMA) and poly(BnMA) were synthesized by single monomer unit insertion and the kinetics and byproducts of degradation investigated by in situ 1H NMR analysis at 70 °C. Trithiocarbonate degradation was ultimately shown to occur by N-phenyl-promoted, N-5 nucleophilic attack on the terminal thiocarbonyl by the ultimate methacrylamide unit.
- Abel, Brooks A.,McCormick, Charles L.
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p. 465 - 474
(2016/02/05)
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- Disulfides as Sulfonylating Precursors for the Synthesis of Sulfone-Containing Oxindoles
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The first facile one-pot synthesis of sulfone-containing oxindoles with easily accessible disulfides as the sulfonylating precursors is described. This reaction occurs smoothly under transition metal-free conditions and shows excellent functional group tolerance, allowing the facile and efficient green synthesis of various sulfone-containing oxindoles in aqueous solution. Preliminary mechanistic studies reveal that both water (H2O) and potassium persulfate (K2S2O8) can be the oxygen source of the sulfone groups in the products. (Figure presented.).
- Zhang, Ming-Zhong,Ji, Peng-Yi,Liu, Yu-Feng,Xu, Jing-Wen,Guo, Can-Cheng
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supporting information
p. 2976 - 2983
(2016/09/16)
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- High-valent palladium-promoted formal Wagner-Meerwein rearrangement
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An oxy-palladation, formal Wagner-Meerwein rearrangement and fluorination cascade has been established for generating fluorinated oxazolidine-2,4-diones and oxazolidin-2-ones. The reaction has a broad substrate scope in which both aryl and alkyl groups can be utilized as efficient migrating groups. Experimental evidence suggests that the reaction is initiated by anti-oxy-palladation of the olefin, followed by oxidative generation of an alkyl PdIV intermediate and a concerted migration-fluorination.
- Wu, Hongmiao,Yang, Bin,Zhu, Lin,Lu, Ronghua,Li, Guigen,Lu, Hongjian
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supporting information
p. 5804 - 5807
(2016/11/29)
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- Synthesis of Oxindoles by Bronsted Acid Catalyzed Radical Cascade Addition of Ketones
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Oxindoles bearing ketone side chains in the 3-position can be synthesized by Bronsted acid catalysis from N-aryl methacrylamides, ketones, and hydroperoxides. The cyclized products are presumably formed in a radical cascade reaction, initiated by decay of intermediate alkenyl peroxides. In the case of acrylic substrates that do not undergo cyclization, γ-peroxyketones were isolated instead, indicating that the final cyclization step of the cascade does not take place in these cases.
- Boess, Esther,Karanestora, Sofia,Bosnidou, Alexandra-Eleni,Schweitzer-Chaput, Bertrand,Hasenbeck, Max,Klussmann, Martin
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supporting information
p. 1973 - 1976
(2015/09/01)
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- Metal-free arylalkylation of N -aryl acrylamides with azobisalkylnitriles
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A novel metal-free arylalkylation of N-aryl acrylamides with readily available azobisalkylnitriles leading to cyano-containing oxindoles has been developed. The use of readily available azobisalkylnitriles and DTBP as oxidant makes this protocol environmentally benign and practical.
- Tian, Qingshan,He, Ping,Kuang, Chunxiang
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supporting information
p. 681 - 687
(2015/03/14)
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- Light-induced BiOBr nanosheets accelerated highly regioselective intermolecular trifluoromethylation/arylation of alkenes to synthesize CF3-containing aza-heterocycles
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A light-induced, BiOBr nanosheets accelerated intermolecular one-pot tandem trifluoromethylation/arylation of alkenes was presented. With this method, a series of CF3-containing aza-heterocycles with high selectivity were fabricated in moderate to good yields. Preliminary mechanistic studies revealed that the exceptional transformation was originated from the synergistic effect of photogenerated electrons and holes. Density function theory (DFT) was adopted to understand the high selectivity of this photocatalytic chemical transformation.
- Liu, Cuibo,Zhao, Weiwei,Huang, Yi,Wang, Hongming,Zhang, Bin
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supporting information
p. 4344 - 4351
(2015/06/08)
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- UV light-mediated difunctionalization of alkenes through aroyl radical addition/1,4-/1,2-Aryl shift cascade reactions
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UV light-mediated difunctionalization of alkenes through an aroyl radical addition/1,4-/1,2-aryl shift has been described. The resulted aroyl radical from a photocleavage reaction added to acrylamide compounds followed by cyclization led to the formation of oxindoles, whereas the addition to cinnamic amides aroused a unique 1,4-aryl shift reaction. Furthermore, the difunctionalization of alkenes of prop-2-en-1-ols was also achieved through aroyl radical addition and a sequential 1,2-aryl shift cascade reaction.
- Zheng, Lewei,Huang, Hongli,Yang, Chao,Xia, Wujiong
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supporting information
p. 1034 - 1037
(2015/03/30)
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- Efficient cu-catalyzed atom transfer radical addition reactions of fluoroalkylsulfonyl chlorides with electron-deficient alkenes induced by visible light
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Fluoroalkylsulfonyl chlorides, RfSO2Cl, in which Rf=CF3, C4F9, CF2H, CH2F, and CH2CF3, are used as a source of fluorinated radicals to add fluoroalkyl groups to electron-deficient, unsaturated carbonyl compounds. Photochemical conditions, using Cu mediation, are used to produce the respective α-chloro-β-fluoroalkylcarbonyl products in excellent yields through an atom transfer radical addition (ATRA) process. Facile nucleophilic replacement of the α-chloro substituent is shown to lead to further diverse functionalization of the products.
- Tang, Xiao-Jun,Dolbier, William R.
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supporting information
p. 4246 - 4249
(2015/04/14)
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- Oxidant-Free Rhodium(I)-Catalyzed Difunctionalization of Acrylamide: An Efficient Approach to Synthesize Oxindoles
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(Figure Presented) The first rhodium(I)-catalyzed difunctionalization of arylacrylamides to synthesize oxindoles is developed, and it does not require the assistance of an oxidant. This method provides an efficient approach to generate various useful functionalized oxindoles, some of which cannot be easily accessed by previous approaches.
- Li, Chen-Chen,Yang, Shang-Dong
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supporting information
p. 2142 - 2145
(2015/05/13)
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- Visible-Light Photoredox Catalysis: Direct Synthesis of Sulfonated Oxindoles from N-Arylacrylamides and Arylsulfinic Acids by Means of a Cascade C-S/C-C Formation Process
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A novel photocatalytic synthesis of sulfonated oxindoles from N-arylacrylamides and arylsulfinic acids was developed by means of a cascade C-S/C-C bond-formation process. This method provides mild, efficient, and atom-economical access to various sulfonated oxindoles in water. Let there be light! A novel photocatalytic synthesis of sulfonated oxindoles from N-arylacrylamides and arylsulfinic acids was developed by means of a cascade C-S/C-C bond-formation process. This method provides mild, efficient, and atom-economical access to various sulfonated oxindoles in water (see scheme).
- Xia, Dong,Miao, Tao,Li, Pinhua,Wang, Lei
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p. 1919 - 1925
(2015/09/07)
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- Direct Photoredox-Catalyzed Reductive Difluoromethylation of Electron-Deficient Alkenes
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Photoredox-catalyzed reductive difluoromethylation of electron-deficient alkenes was achieved in one step under tin-free, mild and neutral conditions. This protocol affords a facile method to introduce RCF2 (R=H, Ph, Me, and CH2N3) groups at sites β to electron-withdrawing groups. It was found that TTMS (tris(trimethylsilyl)silane) served nicely as both the H-atom donor and the electron donor in the catalytic cycle. Experimental and DFT computational results provided evidence that RCF2 (R=H, Ph, Me) radicals are nucleophilic in nature.
- Tang, Xiao-Jun,Zhang, Zuxiao,Dolbier, William R.
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supporting information
p. 18961 - 18965
(2016/01/26)
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- Hydrazonyl Radical-Participated Tandem Reaction: A Strategy for the Synthesis of Pyrazoline-Functionalized Oxindoles
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An efficient and practical tandem cyclization/addition/cyclization strategy is developed for the initial generated hydrazonyl radicals derived from the oxidation of β,γ-unsaturated hydrazones. By using this protocol, structurally novel pyrazoline-functionalized oxindoles are prepared by the reaction of easily accessible β,γ-unsaturated hydrazones with N-aryl acrylamides under the metal- and solvent-free conditions of DTBP (di-tert-butyl peroxide) via a tandem intra/intermolecular C-N/C-C/C-C bond formation.
- Duan, Xiao-Yong,Yang, Xiu-Long,Jia, Pan-Pan,Zhang, Man,Han, Bing
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supporting information
p. 6022 - 6025
(2016/01/09)
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- Metal-free nitro-carbocyclization of activated alkenes: A direct approach to synthesize oxindoles by cascade C-N and C-C bond formation
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A novel and direct metal-free nitro-carbocyclization of activated alkenes leading to valuable nitro-containing oxindoles via cascade C-N and C-C bond formation has been developed. The mechanistic study indicates that the initial NO and NO2 radical addition and the following C-H functionalization processes are involved in this transformation. The Royal Society of Chemistry 2014.
- Shen, Tao,Yuan, Yizhi,Jiao, Ning
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supporting information
p. 554 - 556
(2014/01/06)
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- Iron-catalyzed aerobic difunctionalization of alkenes: A highly efficient approach to construct oxindoles by C-S and C-C bond formation
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A novel iron-catalyzed efficient approach to construct sulfone-containing oxindoles, which play important roles in the structural library design and drug discovery, has been developed. The use of readily available benzenesulfinic acids, an inexpensive iron salt as the catalyst, and air as the oxidant makes this sulfur incorporation protocol very efficient and practical. This journal is the Partner Organisations 2014.
- Shen, Tao,Yuan, Yizhi,Song, Song,Jiao, Ning
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supporting information
p. 4115 - 4118
(2014/04/03)
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- Arylnitration of alkenes by nitration/C-H functionalization cascade using AgNO3 and HOAc
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A novel arylnitration of alkenes by nitration and C-H functionalization cascade process has been developed. This methodology provides an efficient way to construct a variety of nitro-containing oxindoles and dihydroquinolin-2(1H)- ones. In addition, the process exhibits significant functional group tolerance. Moreover, the use of inexpensive and readily available starting materials makes this practical and atom-economical approach particularly attractive.
- Li, Ya-Min,Shen, Yuehai,Chang, Kwen-Jen,Yang, Shang-Dong
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supporting information
p. 2119 - 2122
(2014/04/03)
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- Arylnitration of alkenes by nitration/C-H functionalization cascade using AgNO3 and HOAc
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A novel arylnitration of alkenes by nitration and C-H functionalization cascade process has been developed. This methodology provides an efficient way to construct a variety of nitro-containing oxindoles and dihydroquinolin-2(1H)-ones. In addition, the process exhibits significant functional group tolerance. Moreover, the use of inexpensive and readily available starting materials makes this practical and atom-economical approach particularly attractive.
- Li, Ya-Min,Shen, Yuehai,Chang, Kwen-Jen,Yang, Shang-Dong
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supporting information
p. 2119 - 2122
(2015/03/18)
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- The carbomethylation of arylacrylamides leading to 3-ethyl-3-substituted indolin-2-one by cascade radical addition/cyclization
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An FeCl2-promoted carbomethylation of arylacrylamides by di-tert-butyl peroxide (DTBP) is achieved, leading to 3-ethyl-3-substituted indolin-2-one in high yield. The reaction tolerates a series of functional groups, such as cyano, nitro, ethyloxy carbonyl, bromo, chloro, and trifluoromethyl groups. The radical methylation and arylation of the alkenyl group are involved in this reaction. This journal is the Partner Organisations 2014.
- Dai, Qiang,Yu, Jintao,Jiang, Yan,Guo, Songjin,Yang, Haitao,Cheng, Jiang
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supporting information
p. 3865 - 3867
(2014/04/03)
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- Synthesis of oxindoles through silver-catalyzed trifluoromethylation-, difluoromethylation- and arylsulfonylation-cyclization reaction of N-arylacrylamides
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Efficient synthesis of trifluoromethyl and difluoromethyl-substituted oxindoles was achieved by reacting Langlois reagent or Baran reagent with N-arylacrylamides. However, the reaction of aryl sulfinic acid sodium salts with N-arylacrylamides did not give the desulfinative products, instead, aryl sulfonated products were produced. Copyright
- Liu, Jidan,Zhuang, Shaobo,Gui, Qingwen,Chen, Xiang,Yang, Zhiyong,Tan, Ze
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supporting information
p. 3196 - 3202
(2014/06/09)
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- Catalyst-free direct arylsulfonylation of N-arylacrylamides with sulfinic acids: A convenient and efficient route to sulfonated oxindoles
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A simple, efficient and catalyst-free procedure has been developed for the construction of sulfonated oxindoles via the direct arylsulfonylation of N-arylacrylamides with sulfinic acids. The present protocol, which simply utilizes cheap oxidants, readily-available starting materials, and catalyst-free conditions, provides an alternative and highly attractive approach to a series of sulfonated oxindoles with high atom efficiency and excellent functional group tolerance. This journal is the Partner Organisations 2014.
- Wei, Wei,Wen, Jiangwei,Yang, Daoshan,Du, Juan,You, Jinmao,Wang, Hua
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supporting information
p. 2988 - 2991
(2014/06/10)
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