- Influence of the substituent D/A at the 1,2,3-triazole ring on novel terpyridine derivatives: Synthesis and properties
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In this study, we newly designed and developed a synthesis route based on the 1,3-dipolar cycloaddition of the derivatives of 4′-(1,2,3-triazol-4-yl)phenyl-2,2′:6′,2′′-terpyridine with various (hetero)aryl substituents, differing in electronic character, on a triazol ring. The obtained compounds were comprehensively characterized by UV-Vis spectroscopy and electrochemical and thermal studies. Moreover, preliminary biological tests were conducted. The investigation allowed the selection of materials with the most promising properties with particular emphasis on the nature of the substituents. In addition, theoretical studies (DFT and TD-DFT) were performed to verify the comprehensive understanding of experimental results.
- Zych, Dawid,Slodek, Aneta,Zimny, D?astin,Golba, Sylwia,Malarz, Katarzyna,Mrozek-Wilczkiewicz, Anna
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Read Online
- A curcumin-analogous fluorescent sensor for cysteine detection with a bilateral-response click-like mechanism
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A novel curcumin-analogous fluorescent sensor, DNP, was developed for cysteine detection with a bilateral-response click-like mechanism. DNP indicated high selectivity and practical sensitivity. It could recognize Cys from other biologically relevant molecules, especially, from GSH and Hcy. The most interesting point was that, with typical azide groups for sensing, DNP indicated a covalent binding procedure with Cys instead of a presupposed simple reduction for reductive sulfide. Moreover, the recognition occurred at both sides of the sensor. DNP could be utilized into the detection of endogenous and exogenous Cys in living cells. Though the specific optical performances of DNP still need optimization, this work supplied novel information for broadening the vision on fluorophores and mechanisms, for the monitoring of Cys and even other sulfur-containing species.
- Fan, Xiang-Jun,Fang, Fang,Li, Zhen,Liu, Sheng-Jin,Yang, Yu-shun
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Read Online
- One-pot synthesis of biopolymeric hollow nanospheres by photocrosslinking
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Biopolymeric hollow nanospheres with stabilized structure have been prepared by self-assembly of amphiphatic photocrosslinkable carboxymethyl chitosans in a water medium into hollow nanocapsules and subsequent in situ photo-crosslinking of the photoreactive functional groups in the shells of the nanocapsules.
- Yin, Yihua,Xu, Sha,Chang, Dan,Zheng, Hua,Li, Junli,Liu, Xiaoping,Xu, Peihu,Xiong, Fuliang
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Read Online
- A colorimetric and ratiometric fluorescent probe with a large stokes shift for detection of hydrogen sulfide
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Developing probes for selective and sensitive detection of hydrogen sulfide (H2S) has received much research attention, because H2S is an environmental toxin as well as an important signaling molecule to regulate physiological and pathological processes. In this work, a new colorimetric and ratiometric fluorescent probe (Probe 1) for H2S detection was synthesized by employing dicyanoisophorone based fluorescence dye as a fluorophore and azide group as the response unit. The synthesized Probe 1 showed a long emission wavelength (λem = 643 nm) and large stokes shift (λem - λabs = 163 nm). Based on the H2S-induced reduction of azide group to amino group, Probe 1 showed high response speed, sensitivity, and selectivity toward HS- under room temperature. Moreover, Probe 1 can ratiometrically respond to HS- and the detection limit is as low as 0.13 μM. It was proved that Probe 1 is suitable for quantitatively detecting HS- ions in river water samples. The numerous advantages of Probe 1 make it be potentially used for quantitative detection of H2S in environment and living organisms.
- Xiang, Kaiqiang,Liu, Yunchang,Li, Changjiang,Tian, Baozhu,Tong, Tianzhong,Zhang, Jinlong
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Read Online
- First triazole-linked porphyrin-fullerene dyads
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(Chemical Equation Presented)A general procedure for the synthesis of 1,2,3-triazole-linked porphyrin-fullerene dyads is described. Four of these compounds have been prepared and characterized.
- Fazio, Michael A.,Lee, Olivia P.,Schuster, David I.
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Read Online
- In vivo targeted delivery of antibodies into cancer cells with pH-responsive cell-penetrating poly(disulfide)s
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Cell-penetrating poly(disulfide)s (CPDs) are promising vehicles for cytosolic delivery of proteins. However, currently available arginine-rich CPD has rarely been reported for systemic delivery due to its "always"positive charge. Herein, we developed pH-r
- Dai, Xiaoyang,Kong, Yulong,Liao, Jia-Yu,Qian, Linghui,Shao, Jinning,Wang, Wenchao,Weng, Qinjie,Yan, Jiaqi,Yao, Shao Q.,Zeng, Kui,Zeng, Su,Zhang, Ying
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supporting information
p. 1314 - 1317
(2022/02/05)
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- Nucleophilic transformations of azido-containing carbonyl compoundsviaprotection of the azido group
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Nucleophilic transformations of azido-containing carbonyl compounds are discussed. The phosphazide formation from azides and di(tert-butyl)(4-(dimethylamino)phenyl)phosphine (Amphos) enabled transformations of carbonyl groups with nucleophiles such as lithium aluminum hydride and organometallic reagents. The good stability of the phosphazide moiety allowed us to perform consecutive transformations of a diazide through triazole formation and the Grignard reaction.
- Aimi, Takahiro,Meguro, Tomohiro,Kobayashi, Akihiro,Hosoya, Takamitsu,Yoshida, Suguru
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supporting information
p. 6062 - 6065
(2021/06/21)
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- Photoredox-Catalyzed Four-Component Reaction for the Synthesis of Complex Secondary Amines
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The one-pot sulfonylation/aminoalkylation of styrene derivatives furnishing substituted ?3-sulfonylamines was accomplished through a photoredox-catalyzed four-component reaction. Besides one molecule of water and the sodium counterion of the sulfinate, all atoms of the starting materials are transferred to the final product, rendering this process highly atom-efficient. The operationally simple protocol allows for the simultaneous formation of three new single bonds (C-S, C-N, and C-C) and therefore grants rapid access to structurally diverse products.
- Kammer, Lisa Marie,Krumb, Matthias,Spitzbarth, Benjamin,Lipp, Benjamin,Kühlborn, Jonas,Busold, Jonas,Mulina, Olga M.,Terentev, Alexander O.,Opatz, Till
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supporting information
p. 3318 - 3322
(2020/03/24)
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- COMPOSITIONS COMPRISING ENZYME CLEAVABLE LINKER PLATFORMS AND CONJUGATES THEREOF
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The present invention relates to a cleavable linker platform. In particular, the invention relates to construction of an enzyme cleavable linker platform conjugated to a drug or a diagnostically relevant compound, a biomolecule, and an enzyme cleavable group, for which cleavage of the enzyme cleavable group leads to release of the drug or diagnostically relevant compound.
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Page/Page column 70
(2021/01/23)
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- Synthesis of azido-substituted benzaldehydes via SNAr chemistry
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Conditions for the formation of azidobenzaldehydes and azidobenzonitriles using sodium azide in DMSO under typical SNAr conditions are described. This simplifies access to these valuable building blocks compared to the more common sequences reported in the literature. Interestingly, fluorosubstituted aryl ketones and esters do not afford azides, but instead amine products.
- Kafle, Arjun,Yossef, Sandy,Handy, Scott T.
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supporting information
(2020/04/21)
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- Hydrogen sulfide sensing using an aurone-based fluorescent probe
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Hydrogen sulfide detection and sensing is an area of interest from both an environmental and a biological perspective. While many methods are currently available, the most sensitive and biologically applicable ones are fluorescence based. In general, these fluorescent probes are based upon large, high-molecular weight, well-characterized fluorescent scaffolds that are synthetically demanding to prepare and difficult to tune and modify. In this study, we have reported a new reduction-based, rationally designed and synthesized turn-on fluorescent probe (Z)-2-(4′-azidobenzylidene)-5-fluorobenzofuran-3(2H)-one (6g) utilizing a low molecular weight aurone fluorophore. During these studies, the modular nature of the synthesis was used to quickly overcome problems with solubility, overlap of excitation of the probe and reduced product, and rate of reaction, resulting in a final compound that is efficient and sensitive for the detection of hydrogen sulfide. The limitation of slow reaction and the reduced fluorescence in a biologically relevent medium was solved by employing cationic surfactant cetyltrimethyl ammonium bromide (CTAB). The probe features a high fluorescence enhancement, fast response (10-30 min), and good sensitivity (1 μm) and selectivity for hydrogen sulfide. This journal is
- Bhattarai, Shrijana,Handy, Scott T.,Kafle, Arjun,Miller, Justin M.
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p. 45180 - 45188
(2020/12/30)
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- SNAr azidation of phenolic functions utilizing diphenyl phosphorazidate
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A useful method for the synthesis of aryl azides via SNAr reaction of phenol derivatives using diphenyl phosphorazidate (DPPA) as an azidation reagent was developed. Various phenol derivatives bearing electron-withdrawing groups were converted into the corresponding aryl azides in a single step. This method is easy to perform and enables the preparation of aryl azides without the use of explosive azide sources.
- Ishihara, Kotaro,Shioiri, Takayuki,Matsugi, Masato
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supporting information
(2019/12/27)
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- Acceptor-π-Acceptor-Acceptor/Donor systems containing dicyanovinyl acceptor group with substituted 1,2,3-triazole motif – synthesis, photophysical and theoretical studies
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An efficient synthetic route (target products obtained with yields 65–85%) for obtaining of malononitrile derivatives containing triazole motif substituted in the way providing the electronic architecture Acceptor-π-Acceptor-Acceptor/Donor (–CH2(CN)2/–C6H4–/triazole/substituent) is presented. As the substituents phenyl (A1), p-pentyloxyphenyl (A2), pyrid-2-yl (A3), 9,9-dimethylfluoren-2-yl (A4), 9-octyl-9H-carbazol-3-yl (A5), dibenzo[b,d]thiophen-2-yl (A6) and 2,2′-bithiophenyl-5-yl (A7) were used. The structures of compounds were confirmed by 1H and 13C NMR spectroscopy. The thermal, optical and photophysical properties of obtained target compounds were checked. Understanding of obtained data was supported by quantum-chemical calculations based on DFT methods (time-dependent calculations, NTO analysis, structural parameters). Moreover, the druglikeness analysis was performed based on the commonly known rules.
- Zych, Dawid,Slodek, Aneta
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- Investigating the Impact of Conformational Molecular Engineering on the Crystal Packing of Cavity Forming Porphyrins
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Herein we report the synthesis of 5,10,15,20-tetraaryl-(X)-substituted-2,3,7,8,12,13,17,18-octaethylporphyrins (OETArXPs) and a structural investigation of their solid-state properties via small molecule X-ray diffraction. A series of halogen (fluorine to iodine), nitrogenous (azido, cyano), alkyl (TMS-acetylene and acetylene), and chained (benzyloxy) porphyrins were chosen as the initial target molecules. Following this, a selection of tetravalent metal complexes [Cu(II), Ni(II), and Pd(II)] based on these porphyrins were synthesized to allow for an investigation of the effects of metal complexes on the structural properties of these highly substituted porphyrins. The size of the halogen atom affects the potential of intermolecular interactions and the resulting crystal packing in these 4-halo-OETArXP complexes. The fluorine series have an equal preference for alkyl or aryl groups (ortho-hydrogen), the chlorine series favor interactions between the alkyl groups, and the bromine appears to favor the aryl (ortho- and meta-hydrogens). This results in an extensive cupping pattern in the unit cell. For the 2,6-halo-OETArXP it was established that the change in position alters the types of the intermolecular contacts toward face-to-edge or face-to-face interactions and alters the packing patterns observed. Within the 4-benzyloxy-OETArXP series the meso-substituent favors interacting with the core of the porphyrin macrocycle. The 4-cyano-OETArXP is a suitable hydrogen-bond acceptor and results in an interesting Z-shape network. Additionally, it was highlighted that solvent effects play a much larger role in crystal packing than intermolecular/intramolecular interaction or metal(II) center substitution. This is accompanied by a study using both the azide- and acetylene-OETArXPs as a base molecule to allow for a quick one-step reaction for the generation of a variety of functionalized compounds. Using a copper(I)-catalyzed azide-alkyne cycloaddition reaction, we were able to append hydrogen bonding functionalities to the OETArXPs framework in high yields. The crystal packing images included in this work shows the potential to create selective and functional receptor sites based on free base porphyrins. However, insofar as analytical measurements indicate, the design of such a free base porphyrin through crystal engineering has not yet been realized. The variety of porphyrin packing arrangements herein indicates the need for further studies.
- Flanagan, Keith J.,Twamley, Brendan,Senge, Mathias O.
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p. 15769 - 15787
(2019/12/11)
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- COMPOUNS, COMPOSITIONS AND METHODS OF USE
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Herein, compounds, compositions and methods for modulating inclusion formation and stress granules in cells related to the onset of neurodegenerative diseases, musculoskeletal diseases, cancer, ophthalmological diseases, and viral infections are described.
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Page/Page column 123; 144
(2018/07/29)
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- Based on tubulin azido - β - lactam small molecular probe and its preparation method and application (by machine translation)
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The invention discloses a based on tubulin azido - β - lactam small molecular probe and its preparation method and application, which belongs to the field of pharmaceutical chemistry. The invention will be β - lactam nucleus with the azido active unit is combined, simple and efficient. It has the following general structure: The type of probe molecule anticancer activity in vitro experiments show that a variety of tumor cells MCF - 7, MGC - 803, A549 has a certain inhibition effects. In particular the azido - β - lactam probe molecule I - 9 to the MGC - 803 cell activity of the 85 nm. On the other hand, the compounds of the invention with the microtubule protein binding, inhibiting tubulin polymerization, can be used as potential microtubule protein small molecular probe. The invention solves the azido type of microtubule protein probe of less variety, synthetic complex, the problem of high cost, helps to inhibit tubulin polymerization for drug development. (by machine translation)
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Page/Page column 7
(2017/09/01)
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- Alkyne-azide cycloaddition analogues of dehydrozingerone as potential anti-prostate cancer inhibitors: Via the PI3K/Akt/NF-kB pathway
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Herein, we report the isolation and synthetic modification of dehydrozingerone (DHZ, 1), a secondary metabolite present in the rhizome of Zingiber officinale. We synthesized O-propargylated dehydrozingerone, which was subsequently coupled by alkyne-azide cycloaddition (3-20) using click chemistry. The compounds (1-20) were evaluated for their in vitro cytotoxic activity in a panel of three cancer cell lines. Among all the DHZ derivatives, 3, 6, 7, 8, 9 and 15 displayed potent cytotoxic potential with an IC50 value ranging from 1.8-3.0 μM in MCF-7, PC-3 and HCT-116 cell lines. Furthermore, compound 7 has proven to be the most potent cytotoxic compound in all the three distinct cancer cell lines and also demonstrated significant anti-invasive potential in prostate cancer. The mechanistic study of compound 7 showed that it not only suppressed the AKT/mTOR signalling which regulates nuclear transcription factor-NF-kB but also augmented the expression of anti-invasive markers E-cadherin and TIMP. Compound 7 significantly decreased the expression of pro-invasive markers vimentin, MMP-2 and MMP-9, respectively. This study underscores an efficient synthetic approach employed to evaluate the structure-activity relationship of dehydrozingerone (1) in search of potential new anticancer agents.
- Kumar, Chetan,Rasool, Reyaz Ur,Iqra, Zainab,Nalli, Yedukondalu,Dutt, Prabhu,Satti, Naresh K.,Sharma, Neha,Gandhi, Sumit G.,Goswami, Anindya,Ali, Asif
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p. 2115 - 2124
(2017/11/22)
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- A novel triazole derivative of betulinic acid induces extrinsic and intrinsic apoptosis in human leukemia HL-60 cells
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In an attempt to arrive at more potent cytotoxic agent than the bioactive natural product betulinic acid, influence of small structural modifications of its 1, 2, 3 triazole derivatives tethered at C-28 and both C3, C-28 using click chemistry approach has been studied. The chemically characterized triazoles have been screened for in vitro cytotoxicity against four human cancer cell lines HL-60, MiaPaCa-2, PC-3 and A549 which has allowed to identify triazole derivative 28{1N (4-fluoro phenyl)-1H-1, 2, 3-triazol-4-yl} methyloxy betulinic ester having better potency profile than the parent compound with IC50 values in the range of 5-7 μM. It caused disruption of mitochondrial membrane potential, rendered Bcl-2 cleavage, Bax translocation and decrease Bcl-2/Bax ratio. These events are accompanied by activation of caspases -9, -3, which cleave the PARP-1. It also induces caspase-8, which is involved in extrinsic apoptotic pathway. Therefore, it induces apoptosis through both intrinsic and extrinsic pathways in human leukemia HL-60 cells.
- Khan, Imran,Guru, Santosh K.,Rath, Santosh K.,Chinthakindi, Praveen K.,Singh, Buddh,Koul, Surrinder,Bhushan, Shashi,Sangwan, Payare L.
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p. 104 - 116
(2015/12/04)
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- Synthesis and Biochemical Evaluation of 3-Phenoxy-1,4-diarylazetidin-2-ones as Tubulin-Targeting Antitumor Agents
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Structure-activity relationships for a series of 3-phenoxy-1,4-diarylazetidin-2-ones were investigated, leading to the discovery of a number of potent antiproliferative compounds, including trans-4-(3-hydroxy-4-methoxyphenyl)-3-phenoxy-1-(3,4,5-trimethoxyphenyl)azetidin-2-one (78b) and trans-4-(3-amino-4-methoxyphenyl)-3-phenoxy-1-(3,4,5-trimethoxyphenyl)azetidin-2-one (90b). X-ray crystallography studies indicate the potential importance of the torsional angle between the 1-phenyl A ring and 4-phenyl B ring for potent antiproliferative activity and that a trans configuration between the 3-phenoxy and 4-phenyl rings is generally optimal. These compounds displayed IC50 values of 38 and 19 nM, respectively, in MCF-7 breast cancer cells, inhibited the polymerization of isolated tubulin in vitro, disrupted the microtubular structure in MCF-7 cells as visualized by confocal microscopy, and caused G2/M arrest and apoptosis. Compound 90b possessed a mean GI50 value of 22 nM in the NCI60 cell line screen, displayed minimal cytotoxicity, and was shown to interact at the colchicine-binding site on β-tubulin. Phosphate and amino acid prodrugs of both 78b and 90b were synthesized, of which the alanine amide 102b retained potency and is a promising candidate for further clinical development.
- Greene, Thomas F.,Wang, Shu,Greene, Lisa M.,Nathwani, Seema M.,Pollock, Jade K.,Malebari, Azizah M.,McCabe, Thomas,Twamley, Brendan,OBoyle, Niamh M.,Zisterer, Daniela M.,Meegan, Mary J.
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- An aryl azide, and aryl 1, 2, 3 triazole spiro the synthetic method of the compound of
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The invention discloses a synthetic method of aryl azide and an aryl 1, 2, 3-triazole spiro-compound. The method comprises the following steps: adding substituted arylamine into a reaction container, dissolving the arylamine by methanol, adjusting the pH value to 5-8, introducing methyl nitrite, and reacting for 1-3 hours to obtain a reaction liquid; adding sodium azide into the reaction liquid, monitoring the reaction progress by TLC and reacting for 1-5 hours and posttreating to obtain a pure product of the aryl azide I; adding the product of the aryl azide I, oxonium ylide and an organic solvent into the reaction container, monitoring the reaction progress by TLC, reacting for 36-72 hours at 50-70 DEG C and posttreating to obtain the aryl 1, 2, 3-triazole spiro-compound. The aryl azide is synthesized by methyl nitrite which replaces sodium nitrite and carries out a diazo-reaction with hydrochloric acid, so that the method avoids generation of nitric oxide and nitric dioxide in the reaction process, thereby satisfying the concept of green chemistry.
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Paragraph 0075
(2016/10/10)
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- Copper-Mediated Functionalization of Aryl Trifluoroborates
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This paper describes the Cu(OTf)2-mediated coupling of aryl and heteroaryl trifluoroborates with tetrabutylammonium or alkali metal salts to form C-O, C-N, and C-halogen bonds. The reactions proceed under mild conditions (often room temperature over 16 hours) with carboxylate, halide, and azide salts, all nucleophiles that have been underrepresented in the copper cross-coupling literature. Preliminary results show that copper salts bearing weakly coordinating X-type ligands are essential for enabling these transformations to proceed under mild conditions.
- Schimler, Sydonie D.,Sanford, Melanie S.
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supporting information
p. 2279 - 2284
(2016/10/06)
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- An Efficient Copper-Catalyzed One-Pot Synthesis of 1-Aryl-1,2,3-triazoles from Arylboronic Acids in Water under Mild Conditions
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A convenient method for one-pot two-step 1,3-dipolar cycloadditon reaction of arylboronic acid, sodium azide followed with terminal alkynes in the presence of 2-pyrrolecarbaldiminato-Cu(II) complexes catalyst is reported. Various 1-aryl-1,2,3-triazoles were prepared in 63%-97% yields in water at 30C without any additives and avoiding the isolation of unstable aryl azides.
- Hao, Changbo,Zhou, Changjian,Xie, Jianwei,Zhang, Jie,Liu, Ping,Dai, Bin
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supporting information
p. 1317 - 1320
(2015/11/27)
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- Chemoselective reduction of the carbonyl functionality through hydrosilylation: Integrating click catalysis with hydrosilylation in one pot
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Herein we report the chemoselective reduction of the carbonyl functionality via hydrosilylation using a copper(I) catalyst bearing the abnormal N-heterocyclic carbene 1 with low (0.25 mol %) catalyst loading at ambient temperature in excellent yield within a very short reaction time. The hydrosilylation reaction of α,β-unsaturated carbonyl compounds takes place selectively toward 1,2-addition (C=O) to yield the corresponding allyl alcohols in good yields. Moreover, when two reducible functional groups such as imine and ketone groups are present in the same molecule, this catalyst selectively reduces the ketone functionality. Further, 1 was used in a consecutive fashion by combining the Huisgen cycloaddition and hydrosilylation reactions in one pot, yielding a range of functionalized triazole substituted alcohols in excellent yields.
- Roy, Sudipta Raha,Sau, Samaresh Chandra,Mandal, Swadhin K.
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p. 9150 - 9160
(2014/12/11)
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- In vivo and in situ tracking cancer chemotherapy by highly photostable NIR fluorescent theranostic prodrug
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In vivo monitoring of the biodistribution and activation of prodrugs is urgently required. Near infrared (NIR) fluorescence-active fluorophores with excellent photostability are preferable for tracking drug release in vivo. Herein, we describe a NIR prodrug DCM-S-CPT and its polyethylene glycol-polylactic acid (PEG-PLA) loaded nanoparticles as a potent cancer therapy. We have conjugated a dicyanomethylene-4H-pyran derivative as the NIR fluorophore with camptothecin (CPT) as the anticancer drug using a disulfide linker. In vitro experiments verify that the high intracellular glutathione (GSH) concentrations in tumor cells cause cleavage of the disulfide linker, resulting in concomitantly the active drug CPT release and significant NIR fluorescence turn-on with large Stokes shift (200 nm). The NIR fluorescence of DCM-S-CPT at 665 nm with fast response to GSH can act as a direct off-on signal reporter for the GSH-activatable prodrug. Particularly, DCM-S-CPT possesses much better photostability than ICG, which is highly desirable for in situ fluorescence-tracking of cancer chemotherapy. DCM-S-CPT has been successfully utilized for in vivo and in situ tracking of drug release and cancer therapeutic efficacy in living animals by NIR fluorescence. DCM-S-CPT exhibits excellent tumor-activatable performance when intravenously injected into tumor-bearing nude mice, as well as specific cancer therapy with few side effects. DCM-S-CPT loaded in PEG-PLA nanoparticles shows even higher antitumor activity than free CPT, and is also retained longer in the plasma. The tumor-targeting ability and the specific drug release in tumors make DCM-S-CPT as a promising prodrug, providing significant advances toward deeper understanding and exploration of theranostic drug-delivery systems.
- Wu, Xumeng,Sun, Xuanrong,Guo, Zhiqian,Tang, Jianbin,Shen, Youqing,James, Tony D.,Tian, He,Zhu, Weihong
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supporting information
p. 3579 - 3588
(2014/03/21)
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- Fast responding and selective near-IR Bodipy dye for hydrogen sulfide sensing
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A Bodipy based, highly selective probe for hydrogen sulfide has been designed, synthesized and demonstrated to detect H2S in living cells. In this design, the reduction of two arylazido groups change the charge transfer characteristics of the 3,5-distyryl substituents on the Bodipy core, producing a 20 nm bathochromic spectral shift in the absorption band, and quenching of the emission by 85% compared to the original intensity, through photoinduced electron transfer. This journal is the Partner Organisations 2014.
- Ozdemir, Tugba,Sozmen, Fazli,Mamur, Sevcan,Tekinay, Turgay,Akkaya, Engin U.
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supporting information
p. 5455 - 5457
(2014/05/20)
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- Structure-activity relationship of semicarbazone EGA furnishes photoaffinity inhibitors of anthrax toxin cellular entry
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EGA, 1, prevents the entry of multiple viruses and bacterial toxins into mammalian cells by inhibiting vesicular trafficking. The cellular target of 1 is unknown, and a structure-activity relationship study was conducted in order to develop a strategy for target identification. A compound with midnanomolar potency was identified (2), and three photoaffinity labels were synthesized (3-5). For this series, the expected photochemistry of the phenyl azide moiety is a more important factor than the IC50 of the photoprobe in obtaining a successful photolabeling event. While 3 was the most effective reversible inhibitor of the series, it provided no protection to cells against anthrax lethal toxin (LT) following UV irradiation. Conversely, 5, which possessed weak bioactivity in the standard assay, conferred robust irreversible protection vs LT to cells upon UV photolysis.
- Jung, Michael E.,Chamberlain, Brian T.,Ho, Chi-Lee C.,Gillespie, Eugene J.,Bradley, Kenneth A.
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supporting information
p. 363 - 367
(2014/05/06)
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- PROTECTIVE MOLECULES AGAINST ANTHRAX TOXIN
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Disclosed herein inter alia are compositions and methods useful in the treatment of infectious diseases and exposure to toxins.
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Paragraph 0338; 0359
(2014/08/06)
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- A red emission fluorescent probe for hydrogen sulfide and its application in living cells imaging
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Hydrogen sulfide has emerged as an important biological messenger and much attention has been paid to the design of fluorescent probes for H2S to meet the requirement of accurate measurement of H2S. In this work, a new red emission fluorescent probe for H2S was developed based on the reduction reaction of azide with H2S to amine with the fluorophore of dicyanomethylenedihydrofuran because of its long excitation and emission wavelength. The probe has a high selectivity for H2S over competitive anions and sulfide-containing analytes. Finally, the probe was applied to sense H2S in living cells.
- Chen, Tao,Zheng, Yi,Xu, Zhaochao,Zhao, Miao,Xu, Yongnan,Cui, Jingnan
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supporting information
p. 2980 - 2982
(2013/07/05)
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- A near-infrared fluorescent probe for hydrogen sulfide in living cells
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Fluorescent probes for hydrogen sulfide have received considerable attention because of the biological significance of H2S recognized recently. However, near-infrared fluorescent probes for H2S are still rare. In this work, a new near-infrared fluorescent probe for H2S was developed based on the reduction reaction of azide with H2S to amine based on the fluorophore of dicyanomethylene-4H-chromene because of its long excitation and emission wavelength. The probe has a high selectivity for H2S over competitive anions and sulfide-containing analytes. Finally, the probe was applied to sense H2S in living cells.
- Zheng, Yi,Zhao, Miao,Qiao, Qinglong,Liu, Huiying,Lang, Haijing,Xu, Zhaochao
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p. 367 - 371
(2013/07/19)
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- A new family of bioorthogonally applicable fluorogenic labels
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Synthetic procedures for the construction of fluorogenic azido-labels were developed. Photophysical properties were elaborated by experimental and theoretical investigations. Of the newly synthesized fluorogenic and bioorthogonally applicable dyes two were selected on the basis of their fluorogenic performance and further subjected to in vitro and in vivo studies. Both tags exhibited excellent fluorogenic properties as in aqueous medium, the azide form of the selected dyes is virtually non-fluorescent, while their "clicked" triazole congeners showed intense fluorescence. One of these labels showed a very large Stokes shift. To the best of our knowledge this is the first reported case of mega-Stokes type of fluorogenic labels. These studies have justified that these two fluorogenic tags are remarkably suitable for bioorthogonal tagging schemes. The developed synthetic approach together with the theoretical screen of possible fluorogenic tags will enable the generation of libraries of such tags in the future.
- Herner, Andras,Nikic, Ivana,Kallay, Mihaly,Lemke, Edward A.,Kele, Peter
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supporting information
p. 3297 - 3306
(2013/06/05)
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- One-pot synthesis of 1,2,3-triazoles from boronic acids in water using Cu(ii)-β-cyclodextrin complex as a nanocatalyst
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We report here the one-pot synthesis of 1,2,3-triazoles of arylboronic acids in water. An efficient method has been developed for the synthesis of 1,2,3-triazoles via a one-pot reaction of an arylboronic acid with sodium azide in the presence of Cu2-β-CD (CD = Cyclodextrin) as a nanocatalyst in water followed by a click cyclization reaction with an alkyne at room temperature in air without any additives. This method is simple, rapid, and high yielding.
- Kaboudin, Babak,Abedi, Yaghoub,Yokomatsu, Tsutomu
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experimental part
p. 4543 - 4548
(2012/07/17)
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- General copper-catalyzed transformations of functional groups from arylboronic acids in water
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A simple and general copper-catalyzed method has been developed for transformations of various functional groups (i I, i N3, i SO2R, i OH, i NH2, and i NO 2) on aromatic rings from arylboronic acids in water under air. The protocol uses cheap and readily available inorganic salts (KI, NaN3, NaSO2R, NaOH, NaNO2) and aqueous ammonia as the functional-group sources, simple Cu2O/NH3 as the catalyst system, environmentally friendly water as the solvent, and oxygen in air as the oxidant. Importantly, the copper catalyst system in water was recyclable. This study should provide a useful strategy for interconversions of the functional groups on aromatic rings.
- Yang, Haijun,Li, Yong,Jiang, Min,Wang, Junmei,Fu, Hua
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experimental part
p. 5652 - 5660
(2011/06/23)
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- DNA-templated release of functional molecules with an azide-reduction- triggered immolative linker
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Nucleic acid templated reactions have attracted significant attention for nucleic acid sensing. Herein we report a general design which extends the potential of nucleic acid templated reactions to unleash the function of a broad diversity of small molecules such as a transcription factor agonist, a cytotoxic or a fluorophore.
- Gorska, Katarzyna,Manicardi, Alex,Barluenga, Sofia,Winssinger, Nicolas
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supporting information; experimental part
p. 4364 - 4366
(2011/06/19)
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- Triazole bridges as versatile linkers in electron donor-acceptor conjugates
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Aromatic triazoles have been frequently used as π-conjugated linkers in intramolecular electron transfer processes. To gain a deeper understanding of the electron-mediating function of triazoles, we have synthesized a family of new triazole-based electron donor-acceptor conjugates. We have connected zinc(II)porphyrins and fullerenes through a central triazole moiety-(ZnP-Tri-C60)-each with a single change in their connection through the linker. An extensive photophysical and computational investigation reveals that the electron transfer dynamics-charge separation and charge recombination-in the different ZnP-Tri-C60 conjugates reflect a significant influence of the connectivity at the triazole linker. Except for the m4m-ZnP-Tri-C6017, the conjugates exhibit through-bond photoinduced electron transfer with varying rate constants. Since the through-bond distance is nearly the same for all the synthesized ZnP-Tri-C60 conjugates, the variation in charge separation and charge recombination dynamics is mainly associated with the electronic properties of the conjugates, including orbital energies, electron affinity, and the energies of the excited states. The changes of the electronic couplings are, in turn, a consequence of the different connectivity patterns at the triazole moieties.
- De Miguel, Gustavo,Wielopolski, Mateusz,Schuster, David I.,Fazio, Michael A.,Lee, Olivia P.,Haley, Christopher K.,Ortiz, Angy L.,Echegoyen, Luis,Clark, Timothy,Guldi, Dirk M.
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experimental part
p. 13036 - 13054
(2011/10/07)
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- Copper(II)-catalyzed conversion of aryl/heteroaryl boronic acids, boronates, and trifluoroborates into the corresponding azides: Substrate scope and limitations
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We report the copper(II)-catalyzed conversion of organoboron compounds into the corresponding azide derivatives. A systematic series of phenylboronic acid derivatives is evaluated to examine the importance of steric and electronic effects of the sub-stituents on reaction yield as well as functional group compatibility. Heterocyclic substrates are also shown to participate in this mild reaction while compounds incorporating B-C(sp3) bonds are unreactive under the reaction conditions. The copper(II)-catalyzed boronic acid-azide coupling reaction is further extended to both boronate esters and potassium organotrifluoroborate salts. The method described herein complements existing procedures for the preparation of aryl azides from the respective amino, triazene, and halide derivatives and we expect that it will greatly facilitate copper- and ruthenium-catalyzed azide-alkyne cycloaddition reactions for the preparation of diversely functionalized 1-aryl- or 1-heteroaryl-1,2,3- triazoles derivatives. Georg Thieme Verlag Stuttgart.
- Grimes, Kimberly D.,Gupte, Amol,Aldrich, Courtney C.
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experimental part
p. 1441 - 1448
(2010/10/03)
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- Fluorogenic compounds converted to fluorophores by photochemical or chemical means and their use in biological systems
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Fluorophores derived from photoactivatable azide-pi-acceptor fluorogens or from a thermal reaction of an azide-pi-acceptor fluorogen with an alkene or alkyne are disclosed. Fluorophores derived from a thermal reaction of an alkyne-pi-acceptor fluorogen with an azide are also disclosed. The fluorophores can readily be activated by light and can be used to label a biomolecule and imaged on a single-molecule level in living cells.
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Page/Page column 29
(2010/03/02)
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- Controlled and chemoselective reduction of secondary amides
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This communication describes a metal-free methodology involving an efficient and controlled reduction of secondary amides to imines, aldehydes, and amines in good to excellent yields under ambient pressure and temperature. The process includes a chemoselective activation of a secondary amide with triflic anhydride in the presence of 2-fluoropyridine. The electrophilic activated amide can then be reduced to the corresponding iminium using triethylsilane, a cheap, rather inert, and commercially available reagent. Imines can be isolated after a basic workup or readily transformed to the aldehydes following an acidic workup. The amine moiety can be accessed via a sequential reductive amination by the addition of silane and Hantzsch ester hydride in a one-pot reaction. Moreover, this reduction tolerates various functional groups that are usually reactive under reductive conditions and is very selective to secondary amides.
- Pelletier, Guillaume,Bechara, William S.,Charette, Andre B.
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supporting information; experimental part
p. 12817 - 12819
(2010/11/05)
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- Reliable and diverse synthesis of aryl azides through copper-catalyzed coupling of boronic acids or esters with TMSN3
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(Figure Presented) Aryl azide formation: The copper-catalyzed coupling reaction of boronic esters and acids with TMSN3 have been presented as a highly efficient, simple, broadly applicable, and less hazardous methodology for the practi cal synthesis of aryl azides with structural diversity (see scheme).
- Li, Yu,Gao, Lian-Xun,Han, Fu-She
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supporting information; experimental part
p. 7969 - 7972
(2010/09/14)
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- Exploring a pocket for polycycloaliphatic groups in the CXCR3 receptor with the aid of a modular synthetic strategy
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A CXCR3 pocket capable of accommodating polycycloaliphatics was explored using a modular synthetic strategy. The systematic studies reveal that the tricyclic 2-adamantane and bicyclic (iso)bornyl group are efficiently recognized by CXCR3.
- Wijtmans, Maikel,Verzijl, Dennis,van Dam, Cindy M.E.,Bosch, Leontien,Smit, Martine J.,Leurs, Rob,de Esch, Iwan J.P.
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supporting information; scheme or table
p. 2252 - 2257
(2009/12/03)
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- N-Benzyl-3-sulfonamidopyrrolidines as novel inhibitors of cell division in E. coli
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A new small molecule inhibitor of bacterial cell division has been discovered using a high-throughput screen in Escherichia coli. Although the lead screening hit (534F6) exhibited modest inhibition of the GTPase activity of FtsZ (20 ± 5% at 100 μM of compound), a primary target for bacterial cell division inhibitors, several analogs caused potent bacterial growth inhibition with negligible antagonism of FtsZ GTPase activity. A library of analogs has been prepared and several alkyne-tagged photoaffinity probes have been synthesized for use in experiments to elucidate the primary target of this compound.
- Mukherjee, Shubhasish,Robinson, Carolyn A.,Howe, Andrew G.,Mazor, Tali,Wood, Peter A.,Urgaonkar, Sameer,Hebert, Alan M.,RayChaudhuri, Debabrata,Shaw, Jared T.
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p. 6651 - 6655
(2008/09/17)
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- Synthesis and anti-tubulin activity of a 3′-(4-Azidophenyl)-3′- dephenylpaclitaxel photoaffinity probe
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The synthesis and biological evaluation of a novel paclitaxel photoaffinity probe is described. The synthesis involved the preparation of an azide-containing C13 side chain through a Staudinger cycloaddition followed by a lipase-mediated kinetic resolution to obtain the azetidinone in 99% ee. Coupling of the enantiopure side chain precursor to 7-TES-baccatin III and subsequent silyl ether deprotection afforded 3′-(4-azidophenyl)-3′- dephenylpaclitaxel, which was shown to be as active as paclitaxel in tubulin assembly and cytotoxicity assays.
- Spletstoser, Jared T.,Flaherty, Patrick T.,Himes, Richard H.,Georg, Gunda I.
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p. 6459 - 6465
(2007/10/03)
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- Radical Chain Reaction or Benzenethiol with Pentynylthiol Esters: Production of Aldehydes under Stannane/Silane-Free Conditions
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The radical chain reaction of benzenethiol with accessible 4-pentynylthiol esters provides a new stannane/silane-free protocol for the production of aromatic and aliphatic aldehydes. The procedure is especially useful for the aryl and primary aldehydes, even in the presence of substituents highly sensitive to reductive conditions, and is also of some utility for the vinylic and secondary ones, The protocol is instead not applicable to the tertiary aldehydes, owing to preferential alkane-forming decarbonylation, although the tertiary ones derived from bridgehead precursors can still be usefully produced.
- Benati, Luisa,Leardini, Rino,Minozzi, Matteo,Nanni, Daniele,Scialpi, Rosanna,Spagnolo, Piero,Zanardi, Giuseppe
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p. 985 - 990
(2007/10/03)
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- An efficient, simple synthesis of 4-azidobenzaldehyde
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A three-pot synthesis of 4-azidobenzaldehyde from 4-nitrobenzaldehyde in overall yield of 71% is described. The new synthesis is superior in its ease of reproducibility and reduction of waste side products.
- Walton, Richard,Lahti, Paul M.
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p. 1087 - 1092
(2007/10/03)
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- 3H-azepines and related systems. Part 4. Preparation of 3 H-azepin-2-ones and 6H-azepino[2,1-b]quinazolin-12-ones by photo-induced ring expansions of aryl azides
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Photolysis of a series of p-substituted phenyl azides (p-X-C6H4N3; X= CO2Me, CO2Et, CN, CF3, SO2NH2, CO2CHPh2, COMe, CHO, and NO2) in 1:1 (v/v) THF-water solution produces, in the majority of cases, a 5-substituted-3H-azepine-2-one. In a like manner, 3H-azepin-2-one-3-carboxylates can be prepared from 5-substituted-2-azidobenzoates, providing the 5-substituent is electron-withdrawing. 3H-Azepin-2-one mono- and di-carboxylic acids, the former in admixture with decarboxylated material, and 6H-azepino[2,1-b]quinazolin-12-ones, are obtained by irradiation of 2-azidobenzoic acid and of 5-azidoisophthalic acid, respectively. The mode of formation of the azepino-quinazolinones is discussed.
- Lamara, Kaddour,Smalley, Robert K.
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p. 2277 - 2290
(2007/10/02)
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