- Molecular conformational analysis, vibrational spectra, NBO analysis and first hyperpolarizability of (2E)-3-phenylprop-2-enoic anhydride based on density functional theory calculations
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The conformational behavior and structural stability of (2E)-3-phenylprop-2-enoic anhydride were investigated by using density functional theory. Seventeen possible stable conformations of the title compound were determined and verified with their calcula
- Sheena Mary,Raju,Panicker, C. Yohannan,Al-Saadi, Abdulaziz A.,Thiemann, Thies,Van Alsenoy, Christian
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Read Online
- Platinum (IV) Derivatives with Cinnamate Axial Ligands as Potent Agents Against Both Differentiated and Tumorigenic Cancer Stem Rhabdomyosarcoma Cells
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To design an anticancer drug capable of inhibiting not only the proliferation of the differentiated tumor cells but also reducing the tumorigenic capability of cancer stem cells (CSCs), the new PtIV prodrugs with axial cinnamate ligands were sy
- Brabec, Viktor,Kasparkova, Jana,Markova, Lenka,Novohradsky, Vojtech,Zajac, Juraj
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Read Online
- Photocatalytic Oxidative [2+2] Cycloelimination Reactions with Flavinium Salts: Mechanistic Study and Influence of the Catalyst Structure
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Flavinium salts are frequently used in organocatalysis but their application in photoredox catalysis has not been systematically investigated to date. We synthesized a series of 5-ethyl-1,3-dimethylalloxazinium salts with different substituents in the positions 7 and 8 and investigated their application in light-dependent oxidative cycloelimination of cyclobutanes. Detailed mechanistic investigations with a coumarin dimer as a model substrate reveal that the reaction preferentially occurs via the triplet-born radical pair after electron transfer from the substrate to the triplet state of an alloxazinium salt. The very photostable 7,8-dimethoxy derivative is a superior catalyst with a sufficiently high oxidation power (E=2.26 V) allowing the conversion of various cyclobutanes (with Eox up to 2.05 V) in high yields. Even compounds such as all-trans dimethyl 3,4-bis(4-methoxyphenyl)cyclobutane-1,2-dicarboxylate can be converted, whose opening requires a high activation energy due to a missing pre-activation caused by bulky adjacent substituents in cis-position.
- Hartman, Tomá?,Reisnerová, Martina,Chudoba, Josef,Svobodová, Eva,Archipowa, Nataliya,Kutta, Roger Jan,Cibulka, Radek
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p. 373 - 386
(2021/02/01)
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- Ctc-[Pt(NH3)2(cinnamate)(valproate)Cl2] is a highly potent and low-toxic triple action anticancer prodrug
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Pt(iv) prodrugs have gained tremendous attention due to their indisputable advantages compared to cisplatin. Herein, new Pt(iv) derivatives with cinnamic acid at the first axial position, and inhibitor of matrix metalloproteinases-2 and-9, histone deacetylase, cyclooxygenase or pyruvate dehydrogenase at the second axial position are constructed to develop multi-action prodrugs. We demonstrate that Pt(iv) prodrugs are reducible and have superior antiproliferative activity with IC50 values at submicromolar concentrations. Notably, Pt(iv) prodrugs exhibit highly potent anti-tumour activity in an in vivo breast cancer model. Our results support the view that a triple-action Pt(iv) prodrug acts via a synergistic mechanism, which involves the effects of CDDP and the effects of axial moieties, thus jointly leading to the death of tumour cells. These findings provide a practical strategy for the rational design of more effective Pt(iv) prodrugs to efficiently kill tumour cells by enhancing their cellular accumulation and tuning their canonical mechanism.
- Li, Yang,Shi, Shan,Zhang, Shurong,Gan, Zongjie,Wang, Xin,Zhao, Xudong,Zhu, Yijian,Cao, Meiting,Wang, Xiaoyue,Li, Wei
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supporting information
p. 11180 - 11188
(2021/08/25)
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- Isothiourea-Catalyzed Atroposelective N-Acylation of Sulfonamides
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We report herein an atroposelective N-acylation of sulfonamides using a commercially available isothiourea catalyst, (S)-HBTM, with a simple procedure. The N-sulfonyl anilide products can be obtained in good to high enantiopurity, which represents a new axially chiral scaffold. The application of the product as a chiral iodine catalyst is also demonstrated for the asymmetric α-oxytosylation of propiophenone.
- Ong, Jun-Yang,Ng, Xiao Qian,Lu, Shenci,Zhao, Yu
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supporting information
p. 6447 - 6451
(2020/09/02)
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- Rhodium(i)-catalyzed C6-selective C-H alkenylation and polyenylation of 2-pyridones with alkenyl and conjugated polyenyl carboxylic acids
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A versatile Rh(i)-catalyzed C6-selective decarbonylative C-H alkenylation of 2-pyridones with readily available, and inexpensive alkenyl carboxylic acids has been developed. This directed dehydrogenative cross-coupling reaction affords 6-alkenylated 2-pyridones that would otherwise be difficult to access using conventional C-H functionalization protocols. The reaction occurs with high efficiency and is tolerant of a broad range of functional groups. A wide scope of alkenyl carboxylic acids, including challenging conjugated polyene carboxylic acids, are amenable to this transformation and no addition of external oxidant is required. Mechanistic studies revealed that (1) Boc2O acts as the activator for the in situ transformation of the carboxylic acids into anhydrides before oxidative addition by the Rh catalyst, (2) a decarbonylation step is involved in the catalytic cycle, and (3) the C-H bond cleavage is likely the turnover-limiting step.
- Zhao, Haoqiang,Xu, Xin,Luo, Zhenli,Cao, Lei,Li, Bohan,Li, Huanrong,Xu, Lijin,Fan, Qinghua,Walsh, Patrick J.
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p. 10089 - 10096
(2019/11/14)
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- Substituted cinnamic anhydrides act as selective inhibitors of acetylcholinesterase
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Cinnamic anhydrides have been shown to be more than reactive reagents, but they also act as inhibitors of the enzyme acetylcholinesterease (AChE). Thus, out of a set of 33 synthesised derivatives, several of them were mixed type inhibitors for AChE (from electric eel). Thus, (E)-3-(2,4-dimethoxyphenyl)acrylic anhydride (2c) showed Ki = 8.30 ± 0.94 μM and Ki′ = 9.54 ± 0.38 μM, and for (E)-3-(3-chlorophenyl)acrylic anhydride (2u) Ki = 8.23 ± 0.93 μM and Ki′ = 13.07 ± 0.46 μM were measured. While being not cytotoxic to many human cell lines, these compounds showed an unprecedented and noteworthy inhibitory effect for AChE but not for butyrylcholinesterase (BChE).
- Gie?el, Josephine M.,Serbian, Immo,Loesche, Anne,Csuk, René
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- Isothiourea-Catalysed Regioselective Acylative Kinetic Resolution of Axially Chiral Biaryl Diols
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An operationally simple isothiourea-catalysed acylative kinetic resolution of unprotected 1,1′-biaryl-2,2′-diol derivatives has been developed to allow access to axially chiral compounds in highly enantioenriched form (s values up to 190). Investigation of the reaction scope and limitations provided three key observations: i) the diol motif of the substrate was essential for good conversion and high s values; ii) the use of an α,α-disubstituted mixed anhydride (2,2-diphenylacetic pivalic anhydride) was critical to minimize diacylation and give high selectivity; iii) the presence of substituents in the 3,3′-positions of the diol hindered effective acylation. This final observation was exploited for the highly regioselective acylative kinetic resolution of unsymmetrical biaryl diol substrates bearing a single 3-substituent. Based on the key observations identified, acylation transition state models have been proposed to explain the atropselectivity of this kinetic resolution.
- Qu, Shen,Greenhalgh, Mark D.,Smith, Andrew D.
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supporting information
p. 2816 - 2823
(2019/02/05)
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- Organophosphane-Promoted Synthesis of Functionalized α,β-Unsaturated Alkenes and Furanones via Direct β-Acylation
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We report a phosphine-mediated direct β-acylation of α,β-unsaturated 1,3-diketones with acyl chlorides and a base. Functionalized furanones were also prepared by the reaction of cinnamic acid and acyl chloride according to our protocol via β-acylation. Our studies revealed that α,β-unsaturated 1,3-diketones with an electron-donating group at the second position favor the formation of β-acylated products, whereas those with oxygen, such as anhydrides, favor furanones via an unprecedented C-acylation/cyclization sequence.
- Liou, Yan-Cheng,Su, Yin-Hsiang,Ku, Kuan-Chun,Edukondalu, Athukuri,Lin, Chun-Kai,Ke, You-Syuan,Karanam, Praneeth,Lee, Chia-Jui,Lin, Wenwei
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supporting information
p. 8339 - 8343
(2019/10/16)
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- One-pot synthesis of thioesters with sodium thiosulfate as a sulfur surrogate under transition metal-free conditions
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In this paper, we report an efficient synthetic method for thioester formation from sodium thiosulfate pentahydrate, organic halides, and aryl anhydrides. In the one-pot two-step reactions developed in this study, sodium thiosulfate was used as the sulfur surrogate for acylation with anhydrides, followed by substitution with organic halides through the in situ generation of thioaroylate. Furthermore, two important organic compounds could be successfully synthesized using our developed method. The advantages of the one-pot two-step reactions are operational simplicity, structurally diverse products with 42%-90% yields, use of relatively low toxic and odourless reagents, and easy applicability to large-scale operation.
- Liao, Yen-Sen,Liang, Chien-Fu
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supporting information
p. 1871 - 1881
(2018/03/23)
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- TBHP/ n -Bu 4 PBr-Promoted Oxidative Cross-Dehydrogenative Coupling of Aryl Methanols: A Facile Synthesis of Symmetrical Carboxylic Anhydride Derivatives
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A transition-metal-free oxidative cross-dehydrogenative coupling reaction has been developed for the preparation of symmetrical carboxylic anhydrides through self-coupling dual C-O bond formations of aryl methanols. In the presence of a catalytic amount of tetrabutylphosphonium bromide (TBPB) as transfer agent and aqueous tert -butyl hydroperoxide (TBHP) as oxidant and reactant, methylene groups of aryl methanols were efficiently oxidized to C=O and coupled with the peroxide oxygen from TBHP to form a diverse array of symmetrical carboxylic anhydride derivatives.
- Adib, Mehdi,Pashazadeh, Rahim
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supporting information
p. 136 - 140
(2017/12/27)
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- One-pot synthesis of cinnamic anhydrides from cinnamic acids and 6-chloro-2,4-dimethoxy-sec-triazine (CDMT) at room temperature
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Symmetric cinnamic anhydrides were prepared by the reactions of cinnamic acid substrates with 6-chloro-2,4-dimethoxy-sec-triazine. The reactions were performed at room temperature for 15 h. Diverse cinnamic acid substrates bearing electron-withdrawing or -donating groups worked well, providing the corresponding cinnamic anhydrides in moderate-to-good yields.
- Raja, Gabriel Charles Edwin,Son, Yujeong,Kim, Myungjin,Lee, Sunwoo,Oh, Jonghoon
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p. 2449 - 2455
(2017/12/12)
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- A low toxicity synthetic cinnamaldehyde derivative ameliorates renal inflammation in mice by inhibiting NLRP3 inflammasome and its related signaling pathways
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Uncontrolled inflammation is a leading cause of various chronic diseases. Cinnamaldehyde (CA) is a major bioactive compound isolated from the essential oil of the leaves of Cinnamomum osmophloeum kaneh that exhibits anti-inflammatory activity; however, th
- Ka, Shuk-Man,Kuoping Chao, Louis,Lin, Jung-Chen,Chen, Shui-Tein,Li, Wen-Tai,Lin, Chien-Nan,Cheng, Jen-Che,Jheng, Huei-Ling,Chen, Ann,Hua, Kuo-Feng
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- Optimization by Molecular Fine Tuning of Dihydro-β-agarofuran Sesquiterpenoids as Reversers of P-Glycoprotein-Mediated Multidrug Resistance
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P-glycoprotein (P-gp) plays a crucial role in the development of multidrug resistance (MDR), a major obstacle for successful chemotherapy in cancer. Herein, we report on the development of a natural-product-based library of 81 dihydro-β-agarofuran sesquiterpenes (2-82) by optimization of the lead compound 1. The compound library was evaluated for its ability to inhibit P-gp-mediated daunomycin efflux in MDR cells. Selected analogues were further analyzed for their P-gp inhibition constant, intrinsic toxicity, and potency to reverse daunomycin and vinblastine resistances. Analogues 6, 24, 28, 59, and 66 were identified as having higher potency than compound 1 and verapamil, a first-generation P-gp modulator. SAR analysis revealed the size of the aliphatic chains and presence of nitrogen atoms are important structural characteristics to modulate reversal activity. The present study highlights the potential of these analogues as modulators of P-gp mediated MDR in cancer cells.
- Callies, Oliver,Sánchez-Ca?ete, María P.,Gamarro, Francisco,Jiménez, Ignacio A.,Castanys, Santiago,Bazzocchi, Isabel L.
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supporting information
p. 1880 - 1890
(2016/03/22)
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- Metal-free cross-dehydrogenative coupling of aryl aldehydes to give symmetrical carboxylic anhydrides promoted by the TBHP/nBu4PBr system
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A novel, efficient, and metal-free dual C–O bond formation reaction for the synthesis of carboxylic anhydrides from aryl aldehydes via cross-dehydrogenative coupling is described. Heating a mixture of aromatic aldehydes and an aqueous solution of tert-butyl hydroperoxide as oxidant in the presence of catalytic nBu4PBr in chlorobenzene at 80?°C for 3?h afforded the corresponding carboxylic anhydrides in good to excellent yields.
- Adib, Mehdi,Pashazadeh, Rahim,Rajai-Daryasarei, Saideh,Mirzaei, Peiman,Jamal Addin Gohari, Seyed
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supporting information
p. 3071 - 3074
(2016/07/06)
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- Facile and direct synthesis of symmetrical acid anhydrides using a newly prepared powerful and efficient mixed reagent
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An efficient mixed reagent for direct synthesis of symmetrical carboxylic anhydrides from carboxylic acids has been prepared. Carboxylic acids are converted to anhydrides using triphenylphosphine/ trichloroisocyanuric acid under mild reaction conditions at room temperature. Short reaction time, excellent yields of products, low cost, availability of reagents, simple experimental procedure, and easy work-up of the products are the main advantages of the presented method.
- Rouhi-Saadabad, Hamed,Akhlaghinia, Batool
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p. 479 - 485
(2015/01/30)
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- Rhodium-catalyzed decarbonylative direct olefination of arenes with vinyl carboxylic acids
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A rhodium(I)-catalyzed direct C-H bond olefination of pyridyl-substituted arenes with readily available vinyl carboxylic acids has been realized. This reaction occurred efficiently without the need for any external oxidant, affording the ortho-olefinated products in high yields and excellent regioselectivities. Diversely substituted vinyl carboxylic acids behaved as efficient olefination reagents under the reaction conditions, and a range of functional groups in both coupling partners was well tolerated. Mechanistic studies indicated that a decarbonylation step is involved in this catalytic process, and pivalic anhydride [(t-BuCO)2O] acts as the activator of the carboxylic acids for the in situ generation of highly active anhydrides.
- Qiu, Ruiying,Zhang, Lingjuan,Xu, Conghui,Pan, Yixiao,Pang, Hongze,Xu, Lijin,Li, Huanrong
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supporting information
p. 1229 - 1236
(2015/04/22)
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- Synthesis of symmetric anhydrides using visible light-mediated photoredox catalysis
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A new approach to anhydride formation is reported via activation of C-O bonds by the Vilsmeier-Haack reagent formed by Ru(bpy)3Cl2 and CBr4 in DMF. Various aryl and alkyl carboxylic acids are converted to the corresponding anhydrides in excellent yields.
- Konieczynska, Marlena D.,Dai, Chunhui,Stephenson, Corey R. J.
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supporting information; experimental part
p. 4509 - 4511
(2012/07/31)
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- A mild, clean, and simple synthesis of symmetrical carboxylic anhydrides from carboxylic acides using a polymer supported tosyl chloride
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The use of polymeric reagents simplifies routine acylation of carboxylic acid because it eliminates the traditional purification. We describe the use of readily available cross-linked poly(4-vinylpyridine) supported tosyl chloride, [P4VP].TsCl, in the suspended solution phase synthesis of symmetrical anhydrides from carboxylic acids in the presence of K2CO3 in high yields and purity. The products can be obtained by filtration and evaporation of the solvent.
- Zarchi, M. A. Karimi,Mirjalili,Kahrizsangi, Z. Shamsi,Tayefi
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experimental part
p. 455 - 460
(2010/08/20)
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- Simple preparation of symmetrical carboxylic acid anhydrides by means of Na2CO3/SOCl2
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A convenient and general method for the synthesis of symmetrical carboxylic acid anhydrides using sodium carbonate/thionyl chloride is described. Copyright Taylor & Francis Group, LLC.
- Kazemi,Kiasat,Mombaini
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p. 3219 - 3223
(2008/02/12)
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- PROCESS FOR PRODUCING ACID ANHYDRIDE
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According to the present invention there is provided a process for producing an acid anhydride by reacting a carboxylic acid, preferably a carboxylic acid having a polymerizable group, with a sulfonyl halide compound in the presence of a tertiary amine or in the presence of a tertiary amine and an inorganic base, wherein the tertiary amine or the tertiary amine and the inorganic base are used in an amount of 0.9 to 1.2 equivalents relative to the acid generated from the sulfonyl halide compound.
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- Novel enzymatic synthesis of 4-O-cinnamoyl quinic and shikimic acid derivatives
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The first direct synthesis of 4-O-cinnamoyl derivatives of quinic and shikimic acids were accomplished by regioselective esterification with Candida antarctica lipase A. For hydrocinnamic esters, enzymatic transesterification with vinyl esters gave excell
- Armesto, Nuria,Ferrero, Miguel,Fernandez, Susana,Gotor, Vicente
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p. 5784 - 5787
(2007/10/03)
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- Facile synthesis of carboxylic anhydrides using 4,5-dichloro-2-[(4-nitrophenyl)sulfonyl]pyridazin-3(2H)-one
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A novel and facile synthesis of carboxylic anhydrides from carboxylic acid using 4,5-dichloro-2-[(4-nitrophenyl)sulfonyl]pyridazin-3(2H)-one (2) is presented. Treatment of aliphatic or aromatic carboxylic acids with 2 in the presence of base in organic solvents gave the corresponding anhydrides in good or excellent yields.
- Kim, Jeum-Jong,Park, Yong-Dae,Song Lee, Woo,Cho, Su-Dong,Yoon, Yong-Jin
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p. 1517 - 1520
(2007/10/03)
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- A convenient method for synthesis of symmetrical acid anhydrides from carboxylic acids with trichloroacetonitrile and triphenylphosphine
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Various carboxylic acids are converted into the corresponding carboxylic acid anhydrides treated with trichloroacetonitrile and triphenylphosphine in the presence of triethylamine at room temperature.
- Kim,Jang
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p. 395 - 399
(2007/10/03)
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- 2-Chloro-1,3-dimethylimidazolinium chloride. 1. A powerful dehydrating equivalent to DCC
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2-Chloro-1,3-dimethylimidazolinium chloride (DMC) (3) can act as a powerful dehydrating agent, replacing DCC (1) under nearly neutral conditions. Its application to acylation and dehydration is described.
- Isobe, Toshio,Ishikawa, Tsutomu
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p. 6984 - 6988
(2007/10/03)
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- New synthetic technology for the synthesis of hindered α-diazoketones via acyl mesylates
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(equation presented) A mild and reliable one-pot protocol for the elaboration of sterically demanding carboxylic acids into α-diazoketones via acyl mesylates has been developed. Aside from delineating the reaction parameters which render this strategy quite general for hindered carboxylic acids, we have directly proven the existence of the fleeting acyl mesylate group as the reactive species in these reactions and shed light onto the differing mechanisms which are operative in the activation of hindered and simple carboxylic acids with methanesulfonyl chloride.
- Nicolaou,Baran, Phil S.,Zhong, Yong-Li,Choi, Ha-Soon,Fong, Kin Chiu,He, Yun,Yoon, Won Hyung
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p. 883 - 886
(2008/02/09)
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- Electrochemical generation and reactions of acyloxytriphenylphosphonium ions
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Constant-current electrolysis, in an undivided cell, of Ph3P in the presence of a carboxylic acid in CH2Cl2 containing 2,6-lutidinium perchlorate as the supporting electrolyte was shown to generate the corresponding acyloxyphosphonium ion, Ph3P+-OCOR, which was converted in situ to esters, amides, and β-lactams under mild conditions.
- Ohmori, Hidenobu,Maeda, Hatsuo,Kikuoka, Masayuki,Maki, Toshihide,Masui, Masaichiro
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p. 767 - 776
(2007/10/02)
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- A NEW SYNTHESIS OF CARBOXYLIC AND CARBONIC ACID ANHYDRIDES USING PHASE TRANSFER REACTIONS
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Acyl chlorides and alkylchloroformates smoothly reacted with one molar equivalent of sodium hydroxide, using liquid-liquid phase transfer conditions to afford high yields of the corresponding symmetrical carboxylic and carbonic hemiester anhydrides.Unstable anhydrides such as 4-nitrobenzoic, 2-furoic and methacrylic anhydrides, which are otherwise difficult to obtain, were easily prepared by this method.The reaction mechanism does not seem to involve intermediate hydrolysis of half the acid chloride into the corresponding sodium carboxylate.
- Plusquellec, Daniel,Roulleau, Fabienne,Lefeuvre, Martine,Brown, Eric
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p. 2471 - 2476
(2007/10/02)
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- Facile and Efficient Syntheses of Carboxylic Anhydrides and Amides Using (Trimethylsilyl)ethoxyacetylene
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(Trimethylsilyl)ethoxyacetylene, a stable and easy-handling reagent, serves as an excellent dehydrating agent for the synthesis of carboxylic anhydrides and amides from the corresponding carboxylic acids.By means of this reagent, various types of acid-sensitive carboxylic anhydrides and amides were obtained almost in quantative yields.Twenty-two examples of carboxylic anhydrides and 12 examples of amides were presented.
- Kita, Yasuyuki,Akai, Shuji,Ajimura, Naomi,Yoshigi, Mayumi,Tsugoshi, Teruhisa,et al.
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p. 4150 - 4158
(2007/10/02)
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- ACTIVATION OF A CARBOXY GROUP BY DIALKYL PYROCARBONATES. SYNTHESIS OF SYMMETRICAL ANHYDRIDES AND ARYL ESTERS OF N-PROTECTED AMINO ACIDS USING DI-tert-BUTYL PYROCARBONATE AS CONDENSING REAGENT
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It has been shown that di-tert-butyl pyrocarbonate can be used as a condensing reagent in the production of anhydrides and some aryl esters of carboxylic acids.The synthesis of anhydrides and of phenyl, p-nitrophenyl, β-naphtyl, and quinolin-8-yl esters of N-protected amino acids is described.
- Pozdnev, V. F.,Chernaya, M. Yu.
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p. 333 - 337
(2007/10/02)
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- A MILD AND FACILE SYNTHESIS OF CARBOXYLIC ANHYDRIDES
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Reaction of carboxylic acids with trimethylsilylethoxyacetylene in an inert solvent under mild conditions affords the corresponding carboxylic anhydrides in almost quantitative yields.
- Kita, Y.,Akai, S.,Yoshigi, M.,Nakajima, Y.,Yasuda, H.,Tamura, Y.
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p. 6027 - 6030
(2007/10/02)
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- REAGENTS AND SYNTHETIC METHODS 28. MODIFIED PROCEDURES FOR ANHYDRIZATION, ESTERIFICATION AND THIOLESTERIFICATION OF CARBOXYLIC ACIDS BY MEANS OF AVAILABLE PHOSPHORUS REAGENTS.
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Carboxylic acid anhydrides, esters and thiol esters are obtained by a one-pot method from carboxylic acids and alcohols or thiol by means of phosphorus oxychloride or phenyl dichlorophosphoridate reagents.
- Arrieta, A.,Garcia, T.,Lago, J. M.,Palomo, C.
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p. 471 - 488
(2007/10/02)
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