- Copper-catalyzed annulation of 2-bromobenzoic esters with terminal alkynes towards 3-substituted isocoumarins
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An efficient method for the synthesis of 3-substituted isocoumarins that are an important class of biologically active scaffolds via annulation of 2-bromobenzoic esters with terminal alkynes by copper catalyzed is described. The advantages of this method include mild reaction conditions, high yield and regioselectivity, and wide tolerance toward functional groups.
- Sun, Mengli,Su, Lebin,Dong, Jianyu,Liu, Long,Zhou, Yongbo,Yin, Shuang-Feng
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- AN EFFICIENT ELECTROCHEMICAL SYNTHESIS OF PHENYLETHYNYLCOPPER(I), C6H5CCCu
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Phenylethynylcopper(I) can be prepared in high yield by the oxidation of a copper anode in a solution of phenylacetylene in acetone or acetonitrile.This synthesis represents a significant improvement over existing methods.
- Kumar, Rajesh,Tuck, Dennis G.
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- Photo(electro)catalytic activity enhancement of PhC2Cu by Fe doping induced energy band modulation and luminescence chromism switching
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In this work, iron doping was proposed to improve the photo(electro)catalytic activity of PhC2Cu, an air stable metal-organic coordination polymeric photocatalyst. After displacement of partial Cu atoms by Fe, the energy band structure of PhC2Cu was successively modulated, featuring a narrowed band gap and down-shift in the valence band towards a more positive potential. More interestingly, the luminescence chromism upon iron doping is indicative of inhibited ligand-to-metal charge transfer (LMCT) that is relevant to the recombination of photocarriers. When the mole ratio of Fe/Cu reached 2%, the photocurrent density achieved its maximum, which was 4 times higher than that of the PhC2Cu photocathode, consistent with an enhanced separation of electron-hole pairs. Furthermore, the extremely negative conduction band potential of PhC2Cu enabled efficient O2activation, generating a series of reactive oxygen species (ROS) for the degradation of organic pollutants. The rate of methyl orange (MO) and 2,4-dichlorophenol (2,4-DCP) degradation over 2% Fe-PhC2Cu increased by 2 and 1.6 times. This study provides a promising strategy for improving the activity of metal-organic photocatalysts.
- Qian, Jing,Dang, Wenqiang,Li, Jing,Zhang, Wen,Tian, Meng,Wang, Ning,Song, Wenjing,Lv, Lingling,Jiang, Hai-Ying
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- A highly stable and versatile heterobifunctional fluoroalkylation reagent for preparation of fluorinated organic compounds
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A highly stable heterobifunctional fluoroalkylation reagent, 1-azido-2-chloro-1,1,2-trifluoro-2-iodoethane (ACTI) has been prepared in high yield for the first time by a new method. Moreover, the reactivity of both the azido group and the iodine atom of t
- Dai, Jingwen,Li, Zili,Wang, Taisheng,Bai, Ruke
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- Electrochemical preparation and applications of copper(i) acetylides: A demonstration of how electrochemistry can be used to facilitate sustainability in homogeneous catalysis
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Copper(i) acetylides are important intermediates for many syntheses and have been prepared here electrochemically in an energy efficient manner. These were subsequently employed in simple organic C-C bond forming reactions. We also demonstrate that application of Faraday's laws allows the charge to be calculated so that only the required amount of metal is used. In addition, the application of copper-coated graphite electrodes allows the maximum atom efficiency for this process and even offers a recovery strategy to extract the metal following completion of the reaction.
- Seavill, Peter W.,Holt, Katherine B.,Wilden, Jonathan D.
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- Copper-Catalyzed Decarboxylative Atom Transfer Radical Addition of Iododifluoroacetate to Alkynyl Carboxylic Acids
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The first example of copper-catalyzed decarboxylative atom transfer radical addition of alkynyl carboxylic acids has been developed with a readily available fluoroalkyl halide. This novel protocol has demonstrated a unique difunctionalization of nonterminal alkynes with a broad substrate scope and excellent functional-group tolerance. Mechanistic investigations revealed that the catalytic cycle was initiated by the attack of a difluoroalkyl radical to an in situ generated alkynylcopper species.
- Li, Gang,Cao, Yi-Xuan,Luo, Chen-Guang,Su, Yi-Ming,Li, Yan,Lan, Quan,Wang, Xi-Sheng
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- Sonogashira reactions of alkyl halides catalyzed by NHC [CNN] pincer nickel(II) complexes
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C(carbene)N(amido)N(amine)-pincer nickel(ii) complexes [iPrCNN-Ni-Br] (6), [nBuCNN-Ni-Br] (7) and [BnCNN-Ni-Cl] (8) were synthesized. The catalytic performance of complexes 6-8 for Sonogashira cross-coupling reactions was
- Wang, Zijing,Zheng, Tingting,Sun, Hongjian,Li, Xiaoyan,Fuhr, Olaf,Fenske, Dieter
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- Highly selective copper-catalyzed trifunctionalization of alkynyl carboxylic acids: An efficient route to bis-deuterated β-borylated α,β-styrene
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A copper-catalyzed highly efficient protocol for the synthesis of bis-deuterated β-borylated α,β-styrene derivatives, which can be further transformed to practical isotopically labeled compounds, has been developed. Alkynyl carboxylic acids are employed as alkyne synthons yet demonstrate a sharp discrepancy in reactivity and selectivity compared to terminal alkynes. Meanwhile, this reaction offers a novel and efficient strategy for highly selective trifunctionalization of the carbon-carbon triple bond at ambient temperature.
- Feng, Qiang,Yang, Kai,Song, Qiuling
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- Reaction of alkynylsilanes with CuCl in polar solvents leading to alkynyl group transfer from Si to Cu
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The reaction of 1-phenyl-2-trimethylsilylethyne with CuCl at 80-100°C in N,N-dimethylformamide (DMF) or N,N-dimethylimidazolidinone (DMI) yielded the alkynylcopper species [Cu2Cl(C≡CPh)]n (1) in 56-63% yields. Heating 1 at 80°C under aerobic conditions gave 1,4-diphenyl-1,3-butadiyne in 82% yield via an oxidative coupling of the phenylethynyl ligands.
- Nishihara, Yasushi,Takemura, Miwa,Mori, Atsunori,Osakada, Kohtaro
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- The synthesis and biological activity of novel anthracenone-pyranones and anthracenone-furans
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Abstract An efficient and divergent methodology for the synthesis of new anthracenone-pyranones and anthracenone-furans is described. Key reactions discussed in these syntheses include an aldehyde promoted annulation with a β-keto-sulfoxide, a domino alkyne insertion/carbonylation/Nu-acylation and a DMEDA promoted Castro-Stephens reaction. We also report the in vitro growth inhibition of these compounds in a range of human cancer cells. The natural product BE-26554A displayed good cell growth activity on BE2-C neuroblastoma and SMA glioblastoma cell lines at 0.17 and 0.16 μM (GI50), respectively. Of note, were a CF3 functionalised anthracenone 4-pyranone (chromone) derivative 22, and an anthracenone-furan derivative 54 which displayed 0.20 μM and 0.38 μM growth inhibition, respectively, in the BE2-C neuroblastoma cell line.
- Rixson, James E.,Abraham, James R.,Egoshi, Yuki,Skelton, Brian W.,Young, Kelly,Gilbert, Jayne,Sakoff, Jennette A.,Gericke, Kersten M.,McCluskey, Adam,Stewart, Scott G.
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- Photoredox synthesis of functionalized quinazolinesviacopper-catalyzed aerobic oxidative Csp2-H annulation of amidines with terminal alkynes
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We have developed a visible light-induced photo-redox copper-catalyzed oxidative Csp2-H annulation (Friedel-Crafts-type cyclization) of amidines with terminal alkynes at room temperature to synthesize functionalized quinazolines. We report copp
- Charpe, Vaibhav Pramod,Hwang, Kuo Chu,Ragupathi, Ayyakkannu,Sagadevan, Arunachalam
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supporting information
p. 5024 - 5030
(2021/07/29)
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- Oxy-sulfonylation of terminal alkynesviaC-S coupling enabled by copper photoredox catalysis
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We report the first literature example using visible light-induced trimethylsilyl azide (TMS-N3)-assisted copper-catalyzed oxy-sulfonylation of terminal C-C bonds to form β-keto sulfones (C-S bond formation). TMS-N3promotes the reaction by facilitating the formation of sulfonyl radicals, which later decompose into N2gas upon light irradiation. This method involves the use of commercially available and stable starting materials. Also, a wide range of functional groups have been well-tolerated under the current photoredox process, evading the side product formation. Potent biologically active compounds, such as CES1, 11β-HSD1 inhibitors, anti-analgesic agents, and reactive synthesis intermediates were synthesized to demonstrate the synthetic utility of the current methodology. Moreover, green chemistry metrics and Eco-scale evaluation for the current photochemical method show that the protocol is eco-friendly and highly efficient.
- Charpe, Vaibhav Pramod,Das, Deb Kumar,Hwang, Kuo Chu,Hwu, Jih Ru,Lin, Chun-Cheng,Pampana, V. K. K.,Sagadevan, Arunachalam
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supporting information
p. 3569 - 3574
(2021/06/06)
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- Construction of modular Pd/Cu multimetallic chainsvialigand- And anion-controlled metal-metal interactions
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The presence of Pd?Cu and Pd?Pd interactions as well as the order of metal atoms in a chain held by a modular polynucleating ligand is controlled by the coordinating ability of the anions, leading to selective formation of bi- and tetranuclear Pd/Cu and P
- Deolka, Shubham,Fayzullin, Robert R.,Govindarajan, Ramadoss,Khaskin, Eugene,Khusnutdinova, Julia R.,Pal, Shrinwantu,Rivada-Wheelaghan, Orestes
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supporting information
p. 10206 - 10209
(2021/10/14)
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- Design, Synthesis, and Bioactivities of Phthalide and Coumarin Derivatives Based on the Biosynthesis and Structure Simplification of Gossypol
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Because gossypol and hemigossypol show antiviral activity but are structurally complex, we designed and synthesized a series of structurally simpler phthalide and coumarin derivatives. The phthalide derivatives were synthesized by opening the naphthalene ring of hemigossypol, and the coumarin derivatives were synthesized by ring-opening reactions of the phthalide derivatives with the goal of investigating the effect of the lactone ring size on bioactivity. The bioassay results showed that the two series of target compounds possessed moderate to good activities against tobacco mosaic virus, One of the compounds showed in vivo inactivation, curative, and protection activities of 50 ± 1, 53 ± 3, and 48 ± 2% at 500 mg/L, values which are higher than those of gossypol (32 ± 1, 35 ± 1, 29 ± 1%, respectively) and comparable to those of hemigossypol (55 ± 1, 49 ± 1, and 48 ± 1%, respectively) and the commercial antiviral agent ningnanmycin (56 ± 2, 54 ± 1, 58 ± 1%) at the same dose. Thus, this compound is a promising candidate for the development of new anti-plant-virus agents. In addition, most of the synthesized compounds showed broad-spectrum activity when tested against 14 kinds of phytopathogenic fungi and showed selectivity against Sclerotinia sclerotiorum, Physalospora piricola, and Rhizoctonia cerealis. Moreover, some of the compounds exhibited activity against Plutella xylostella larvae; the two most active compounds exhibited larvicidal activities (LC50) of 4.10 and 5.47 mg/L, respectively. Further studies showed that these compounds also exhibited insecticidal activities against Mythimna separata, Helicoverpa armigera, and Pyrausta nubilalis larvae.
- Guo, Zhonglin,Zhou, Pan,Song, Hongjian,Liu, Yuxiu,Zhang, Jingjing,Li, Yongqiang,Wang, Qingmin
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p. 15123 - 15135
(2021/12/27)
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- Copper-Catalyzed Enantioselective Sonogashira Type Coupling of Alkynes with α-Bromoamides
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An asymmetric copper-catalyzed Sonogashira type coupling between alkynes and α-bromoamides has been developed. This method represents a facile approach to synthetically useful β, γ-alkynyl amides from two readily available starting materials in a highly enantioselective manner. A Bisoxazoline diphenylanaline (BOPA) serves as the effective chiral ligand. Preliminary mechanistic studies support the formation of alkyl radical species.
- Chen, Bin,Mo, Xueling,Zhang, Guozhu
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supporting information
p. 13998 - 14002
(2020/06/10)
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- Visible light-promoted copper catalyzed regioselective acetamidation of terminal alkynes by arylamines
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Herein, we describe a copper photoredox catalyzed synthesis of acetamide via regioselective C-N coupling of arylamines with terminal alkynes using molecular oxygen (O2) as an oxidant at room temperature under visible light irradiation (47 examples). Unique simultaneous formation of both amide and ester functionalities occurs via intramolecular cyclization in a single-step reaction in the case of anthranilic acids using inexpensive copper as a catalyst and eco-friendly O2 as an oxidant and reagent. Different substrates undergo different reaction pathways to generate similar acetamide products, as evidenced by 18O2 labelling experiments. The current protocol was also applied for the rapid, few step preparation of biologically active inhibitors (BACE-1 and PDE4). This process can be readily scaled up to a gram scale, and calculations of green metrics suggest the economic feasibility and eco-friendly nature of the current photoredox approach.
- Pampana, V. Kishore Kumar,Sagadevan, Arunachalam,Ragupathi, Ayyakkannu,Hwang, Kuo Chu
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p. 1164 - 1170
(2020/03/11)
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- Synthesis method of copper-nitrogen heterocyclic carbene complex catalyst
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The invention relates to a synthesis method of a copper-nitrogen heterocyclic carbene complex catalyst. The method mainly solves the problems of low yield, complex purification and the like in the existing synthesis method. According to the technical scheme, the synthesis method of the copper-nitrogen heterocyclic carbene complex catalyst comprises the step that an imidazolium salt is directly reacted with alkynyl copper to obtain the copper-nitrogen heterocyclic carbene complex, the technical problem is well solved, and the synthesis method can be used for scale-up production of the copper-nitrogen heterocyclic carbene complex catalyst.
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Paragraph 0022-0024
(2020/05/14)
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- Cu-Photoredox-catalyzed C(sp)-C(sp3) coupling of redox-active esters with terminal alkynes
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Visible-light-induced C(sp)-C(sp3) coupling of redox-active esters with terminal alkynes has been developed. The activation of carboxylic acids as their redox-active ester derivatives was important for this decarboxylative alkynylation. The strategy established here facilitates the straightforward introduction of triple-bonded functional groups and avoids additional photocatalysts. A wide range of primary, secondary and tertiary acids can be converted into the target products; so this reaction exhibits a broad substrate scope and tolerance of functional groups. Mechanistic experiments suggested that this reaction may undergo a radical process. Under mild reaction conditions, a copper acetylide ligand as a photocatalyst delivered an electron to redox-active ester derivatives, and generated alkyl radicals. The radicals reacted with Cu(ii) to deliver a Cu(iii) complex, and then reductive elimination gave the products.
- Zhang, Dayong,Zhang, Yajing
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p. 4479 - 4483
(2020/10/20)
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- General Synthesis of α-Alkyl Ynones from Morpholine Amides and 1-Copper(I) Alkynes Promoted by Triflic Anhydride
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The first general method for the synthesis of α-alkyl ynones was developed based on the strategy of electrophilic activation of amides. Its distinctive advantages are attributed to the use of air-stable "bare"1-copper(I) alkyne as a mild nucleophile witho
- Weng, Yunxiang,Min, Lin,Zeng, Xiaobao,Shan, Lidong,Wang, Xinyan,Hu, Yuefei
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supporting information
p. 8296 - 8301
(2020/11/03)
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- Copper(II)-Mediated Ring Opening/Alkynylation of Tertiary Cyclopropanols by Using Nonmodified Terminal Alkynes
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The copper(II)-mediated ring opening/alkynylation of cyclopropanol by employing inexpensive and commercially available terminal alkyne is developed. The reactions proceeded efficiently to afford synthetically useful alk-4-yn-1-ones in moderate to good yie
- Cheng, Bu-Qing,Zhang, Si-Xuan,Cui, Yan-Ying,Chu, Xue-Qiang,Rao, Weidong,Xu, Haiyan,Han, Guo-Zhi,Shen, Zhi-Liang
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supporting information
p. 5456 - 5461
(2020/07/14)
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- Copper Photoredox Catalyzed A3’ Coupling of Arylamines, Terminal Alkynes, and Alcohols through a Hydrogen Atom Transfer Process
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The first successful example of the three-component coupling of N-alkylanilines, terminal alkynes, and alcohols was achieved at room temperature by a visible-light-mediated copper-catalyzed photoredox hydrogen-atom transfer process. This method allows pre
- Sagadevan, Arunachalam,Pampana, V. Kishore Kumar,Hwang, Kuo Chu
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supporting information
p. 3838 - 3842
(2019/02/26)
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- Synthesis of Alkynyl Sulfides by Copper-Catalyzed Thiolation of Terminal Alkynes Using Thiosulfonates
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A mild and odorless copper-catalyzed thiolation of terminal alkynes with thiosulfonates is described. The broad substrate scope provides convenient access to a wide variety of sulfur-containing heterocycles. In particular, divergent benzoheteroles are efficiently prepared in a simple manner by thiolation of ethynylbenzenes bearing ortho-nucleophilic functional groups followed by iodocyclization.
- Kanemoto, Kazuya,Yoshida, Suguru,Hosoya, Takamitsu
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supporting information
p. 3172 - 3177
(2019/05/10)
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- Regio- and Stereoselective Synthesis of Enynyl-Aryl Ethers Enabled by Copper/Iodide Tandem Catalysis
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An approach to preparing enynyl-aryl ethers from phenols and phenylacetylenes is described. This method without extra ligands, overcoming the favored Glaser-Hay dimerization of alkyne, features a wide substrate scope (38 examples including endofolliculina
- Wu, Yun-Bin,Xiao, Lin,Mao, Chun-Li,Zang, Zhong-Lin,Zhou, Cheng-He,Cai, Gui-Xin
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supporting information
p. 4461 - 4467
(2019/08/21)
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- Electrochemical synthesis of copper(i) acetylides: Via simultaneous copper ion and catalytic base electrogeneration for use in click chemistry
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We report an efficient and sustainable electrochemical synthesis of copper(i) acetylides using simultaneous copper oxidation and Hofmann elimination of quaternary ammonium salts. The electrochemically-generated base was also regenerated electrochemically,
- Seavill, Peter W.,Holt, Katherine B.,Wilden, Jonathan D.
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p. 29300 - 29304
(2019/09/30)
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- Visible-light induced copper(i)-catalysed denitrogenative oxidative coupling of hydrazinylpyridines with terminal alkynes
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Visible light mediated copper catalysed denitrogenative oxidative coupling of 2-hydrazinopyridines with terminal alkynes to form 2-(alkyl/arylethynyl) pyridines in the presence of O2 at room temperature is reported with 42 examples. This is the first report on visible light stimulated N2 elimination by an in situ generated copper(ii) superoxo/peroxo complex. N2 and water are the only by-products. The green chemistry metrics evaluation signifies that the current method is ecofriendly and economically feasible. This method allows the green synthesis of mGluR5 receptor antagonists, 2-methyl-6-(phenylethynyl)pyridine (MPEP) and 2-((3-methoxyphenyl)ethynyl)-6-methylpyridine (M-MPEP).
- Charpe, Vaibhav Pramod,Hande, Aniket A.,Sagadevan, Arunachalam,Hwang, Kuo Chu
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supporting information
p. 4859 - 4864
(2018/11/21)
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- (Guanidine)copper Complex-Catalyzed Enantioselective Dynamic Kinetic Allylic Alkynylation under Biphasic Condition
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Highly enantioselective allylic alkynylation of racemic bromides under biphasic condition is furnished in this report. This approach employs functionalized terminal alkynes as pro-nucleophiles and provides 6- and 7-membered cyclic 1,4-enynes with high yields and excellent enantioselectivities (up to 96% ee) under mild conditions. Enantioretentive derivatizations highlight the synthetic utility of this transformation. Cold-spray ionization mass spectrometry (CSI-MS) and X-ray crystallography were used to identify some catalytic intermediates, which include guanidinium cuprate ion pairs and a copper-alkynide complex. A linear correlation between the enantiopurity of the catalyst and reaction product indicates the presence of a copper complex bearing a single guanidine ligand at the enantio-determining step. Further experimental and computational studies supported that the alkynylation of allylic bromide underwent an anti-SN2′ pathway catalyzed by nucleophilic cuprate species. Moreover, metal-assisted racemization of allylic bromide allowed the reaction to proceed in a dynamic kinetic fashion to afford the major enantiomer in high yield.
- Cui, Xi-Yang,Ge, Yicen,Tan, Siu Min,Jiang, Huan,Tan, Davin,Lu, Yunpeng,Lee, Richmond,Tan, Choon-Hong
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supporting information
p. 8448 - 8455
(2018/06/22)
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- An Organometallic Cu20 Nanocluster: Synthesis, Characterization, Immobilization on Silica, and "click" Chemistry
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The development of atomically precise nanoclusters (APNCs) protected by organometallic ligands, such as acetylides and hydrides, is an emerging area of nanoscience. In principle, these organometallic APNCs should not require harsh pretreatment for activat
- Cook, Andrew W.,Jones, Zachary R.,Wu, Guang,Scott, Susannah L.,Hayton, Trevor W.
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supporting information
p. 394 - 400
(2018/01/17)
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- Visible Light Copper Photoredox-Catalyzed Aerobic Oxidative Coupling of Phenols and Terminal Alkynes: Regioselective Synthesis of Functionalized Ketones via C C Triple Bond Cleavage
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Direct oxidative coupling of phenols and terminal alkynes was achieved at room temperature by a visible-light-mediated copper-catalyzed photoredox process. This method allows regioselective synthesis of hydroxyl-functionalized aryl and alkyl ketones from simple phenols and phenylacetylene via C C triple bond cleavage. 47 examples were presented. From a synthetic perspective, this protocol offers an efficient synthetic route for the preparation of pharmaceutical drugs, such as pitofenone and fenofibrate.
- Sagadevan, Arunachalam,Charpe, Vaibhav Pramod,Ragupathi, Ayyakkannu,Hwang, Kuo Chu
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supporting information
p. 2896 - 2899
(2017/03/11)
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- General Method for the Synthesis of 1,4-Disubstituted 5-Halo-1,2,3-triazoles
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A general method for the synthesis of 1,4-disubstituted 5-halo-1,2,3-triazoles has been developed. The one-pot two-step process consists of a CuAAC reaction of a copper(I) acetylide with an organic azide catalyzed by (aNHC)CuCl, followed by halogenation with N-chlorosuccinimide, N-bromosuccinimide, or I2.
- Gribanov, Pavel S.,Topchiy, Maxim A.,Karsakova, Iuliia V.,Chesnokov, Gleb A.,Smirnov, Alexander Yu.,Minaeva, Lidiya I.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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supporting information
p. 5225 - 5230
(2017/09/29)
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- Trifluoromethyl- and Fluoroalkylselenolations of Alkynyl Copper(I) Compounds
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The successful perfluoroalkylselenolation of alkynyl copper(I) compounds is described herein. The reaction occurs under oxidant free conditions at room temperature. This convenient one-pot procedure is based on the in situ generation of trifluoromethylsel
- Ghiazza, Clément,Billard, Thierry,Tlili, Anis
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supporting information
p. 10013 - 10016
(2017/08/01)
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- External oxidant-free cross-coupling of arylcopper and alkynylcopper reagents leading to arylalkyne
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External oxidant-free oxidative cross-coupling between arylcopper and alkynylcopper has been performed, which provides a new way for the formation of arylalkyne with high selectivity.
- Wang, Sheng,Min, Yaosen,Zhang, Xiaowei,Xi, Chanjuan
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p. 28308 - 28312
(2017/07/07)
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- Copper(i)-catalysed oxidative C-N coupling of 2-aminopyridine with terminal alkynes featuring a CC bond cleavage promoted by visible light
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Facile visible-light promoted copper-catalyzed aerobic oxidative C-N coupling between 2-aminopyridine and terminal alkynes at room temperature via CC triple bond cleavage is described. This reaction allows direct synthesis of biologically important pyridy
- Ragupathi, Ayyakkannu,Sagadevan, Arunachalam,Lin, Chun-Cheng,Hwu, Jih-Ru,Hwang, Kuo Chu
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supporting information
p. 11756 - 11759
(2016/10/07)
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- Room-Temperature Alkynylation of Phosphine Oxides with Copper Acetylides: Practical Synthesis of Alkynylphosphine Oxides
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An efficient procedure for the synthesis of alkynylphosphine oxides based on the oxidative alkynylation of secondary phosphine oxides with copper acetylides was developed. Activation with molecular oxygen in the presence of either a mixture of 1,2-dimethylimidazole and triethylamine or N-methylimidazole alone enabled the formal umpolung of the poorly nucleophilic copper acetylides, which were coupled with phosphine oxides under remarkably mild conditions. Notable features of this procedure are the availability of the starting materials, its user-friendliness, and its mild conditions, which allow the synthesis of complex alkynylphosphine oxides.
- Gérard, Phidéline,Veillard, Romain,Alayrac, Carole,Gaumont, Annie-Claude,Evano, Gwilherm
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p. 633 - 638
(2017/01/18)
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- Copper Catalysis for Selective Heterocoupling of Terminal Alkynes
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A Cu-catalyzed selective aerobic heterocoupling of terminal alkynes is disclosed, which enables the synthesis of a broad range of unsymmetrical 1,3-diynes in good to excellent yields. The results disprove the long-held belief that homocouplings are exclusively favored in the Glaser-Hay reaction.
- Su, Lebin,Dong, Jianyu,Liu, Long,Sun, Mengli,Qiu, Renhua,Zhou, Yongbo,Yin, Shuang-Feng
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supporting information
p. 12348 - 12351
(2016/10/07)
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- Blue-Emitting Arylalkynyl Naphthalene Derivatives via a Hexadehydro-Diels-Alder Cascade Reaction
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We describe here three alkynyl substituted naphthalenes that display promising luminescence characteristics. Each compound is easily and efficiently synthesized in three steps by capitalizing on the hexadehydro-Diels-Alder (HDDA) cycloisomerization reacti
- Xu, Feng,Hershey, Kyle W.,Holmes, Russell J.,Hoye, Thomas R.
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supporting information
p. 12739 - 12742
(2016/10/13)
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- Photoinduced Copper-Catalyzed Regioselective Synthesis of Indoles: Three-Component Coupling of Arylamines, Terminal Alkynes, and Quinones
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The first successful example of a visible-light-induced copper-catalyzed process for C-H annulation of arylamines with terminal alkynes and benzoquinone is described. This three-component reaction allows use of a variety of commercial terminal alkynes as coupling partners for the one-step regioselective synthesis of functionalized indoles. Moreover, the current process represents a sustainable and atom-economical approach for the preparation of complex indoles from easily accessible starting materials under visible-light irradiation, without the need for expensive metals and harsh reaction conditions.
- Sagadevan, Arunachalam,Ragupathi, Ayyakkannu,Hwang, Kuo Chu
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supporting information
p. 13896 - 13901
(2016/01/25)
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- Cu-promoted sydnone cycloadditions of alkynes: Scope and mechanism studies
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Cu salts have been found to promote the cycloaddition reaction of sydnones and terminal alkynes, providing significant reduction in reaction times. Specifically, the use of Cu(OTf)2 is found to provide 1,3-disubstituted pyrazoles, whereas simpl
- Comas-Barcel?3, Jffllia,Foster, Robert S.,Fiser, B??la,Gomez-Bengoa, Enrique,Harrity, Joseph P. A.
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supporting information
p. 3257 - 3263
(2015/03/05)
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- Convenient and practical alkynylation of heteronucleophiles with copper acetylides
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Copper acetylides, readily available reagents which are characterized by their lack of reactivity, can be simply activated by oxidation with oxygen in the presence of simple nitrogen ligands such as TMEDA or imidazole derivatives. Upon activation, these nucleophilic species undergo a formal umpolung and can transfer their alkyne subunit to a wide range of heteronucleophiles, including amides, oxazolidinones, imines, and dialkyl phosphites. This alkynylation, which provides one of the most practical entry to useful building blocks such as ynamides, ynimines, and alkynylphosphonates, proceeds under especially mild conditions and can be easily performed on a multigram scale. Georg Thieme Verlag Stuttgart, New York.
- Theunissen, Cedric,Lecomte, Morgan,Jouvin, Kevin,Laouiti, Anouar,Guissart, Celine,Heimburger, Jeremy,Loire, Estelle,Evano, Gwilherm
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p. 1157 - 1166
(2014/05/20)
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- Access to difluoromethylated alkynes through the castro-stephens reaction
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An efficient synthesis of difluoromethylated alkynes is described. A panel of readily available CuI acetylides undergo direct difluoromethylation by using BrCF2CO2Et, which is an inexpensive, easy to handle, commercially available fluorinated reagent. The reaction, which is based on a Castro-Stephens transformation, proceeds smoothly under mild conditions offering a new synthetic route for the direct introduction of the difluoromethylated group into alkynes that does not involve ozone-depleting reagents. The resulting products were obtained with good yields by using CsOPiv and Cu(OAc)2 as additives.
- Besset, Tatiana,Poisson, Thomas,Pannecoucke, Xavier
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p. 7220 - 7225
(2015/02/02)
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- Reactions of phenylethynyl cuprates of lanthanides with organyl halides and synthesis of the related polyfunctional compounds
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Phenylethynyl cuprate complexes of lanthanides react with organyl halides RX, Ph3CX, R3SiX, and RC(O)X (X = Cl, I; R = alkyl) in tetrahydrofuran to give polyfunctional organic and hetero-organic compounds with high yield. The reactio
- Zhil'tsov,Druzhkova,Dydykina,Makarov
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p. 2167 - 2173
(2015/02/05)
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- Tandem synthesis of 3-halo-5-substituted isoxazoles from 1-copper(I) alkynes and dihaloformaldoximes
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A tandem synthesis of 3-halo-5-substituted isoxazoles has been developed from 1-copper(I) alkynes and dihaloformaldoximes under base-free conditions. Thus, 1,3-dipolar cycloaddition and all its drawbacks can now be avoided completely.
- Chen, Wenwen,Wang, Bo,Liu, Nan,Huang, Dayun,Wang, Xinyan,Hu, Yuefei
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supporting information
p. 6140 - 6143
(2015/01/09)
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- Rhodium-Catalyzed Direct Oxidative C-H Acylation of 2-Arylpyridines with Terminal Alkynes: A Synthesis of Pyrido[2,1-a]isoindoles
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A synthesis of pyrido[2,1-a]isoindoles is reported by the rhodium-catalyzed direct oxidative CH acylation of 2-aryl pyridines with terminal alkynes. The desired products were obtained in moderate to excellent yields. This is an efficient and clean method to construct C-C/C-N bonds in one step. In addition, the effective rhodium(III) catalyst was isolated and characterized by X-ray crystallography.
- Zhao, Binlin,Yu, Mengxuan,Liu, Hui,Chen, Yu,Yuan, Yu,Xie, Xuejian
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supporting information
p. 3295 - 3301
(2015/02/02)
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- Unprecedented synthesis of alkynylphosphine-boranes through room-temperature oxidative alkynylation
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An original and user-friendly synthesis of alkynylphosphine-boranes, useful building blocks in organic synthesis, based on an oxidative P-alkynylation reaction with readily available copper acetylides is reported. The ability of a secondary phosphine protected with a borane to undergo oxidative coupling without oxidation of the P-moiety is demonstrated for the first time. The reaction, which proceeds at room temperature, is applicable to the preparation of enantioenriched and structurally complex alkynylphosphine-boranes.
- Jouvin, Kevin,Veillard, Romain,Theunissen, Cedric,Alayrac, Carole,Gaumont, Annie-Claude,Evano, Gwilherm
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supporting information
p. 4592 - 4595
(2013/09/24)
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- Oligomerization of phenylferrocenylacetylene under the action of WCl 6
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Phenylferrocenylacetylene was found to be capable of oligomerizing in the presence of WCl6 (130 °C, 24 h) to afford short polyenes (with about 5 monomer units in the macromolecule) in up to ~30% yield. The polyenes synthesized are promising rea
- Tatarinova, Inna V.,Tarasova, Ol'Ga A.,Markova, Marina V.,Morozova, Lyudmila V.,Mikhaleva, Al'Bina I.,Trofimov, Boris A.
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p. 124 - 127
(2012/06/17)
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- Reaction of lanthanide(II) and lanthanide(III) phenylethynyl cuprates with acetyl chloride
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Praseodymium and ytterbium phenylethynyl cuprates [(PhC≡C) 3Cu]3Pr2(THF)6 and {[(PhC≡C)3Cu]?Yb(THF)2}2 react with acetyl chloride in tetrahydrofuran with elimination of phenylethynylcopper and formation of alkoxides [PhC≡C-CCl(CH3)O] n Ln (n = 3, Ln = Pr; n = 2, Ln = Yb). Then praseodymium alkoxide forms ester [methyl (phenylethynyl)chloromethylethanoate] and praseodymium chloride, alkoxy derivative. Itterbium alkoxide is oxidized to unsymmetrical dialkoxyitterbium chloride PhC≡C-CH(CH3)-O-Yb(Cl)-O-CCl(CH3) C≡CPh?2THF.
- Zhil'tsov,Dydykina,Druzhkova
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p. 1767 - 1770
(2011/02/24)
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- Alkynylcopper(i) polymers and their use in a mechanistic study of alkyne-azide click reactions
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Polymeric dinuclear alkynylcopper(i) complexes, for example phenylethynylcopper(i), can be prepared by a robust method involving the interaction of terminal alkynes with copper(ii) salts in acetonitrile. The use of the ladder polymers provides heterogeneous catalysts for copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions and provides important mechanistic information.
- Buckley, Benjamin R.,Dann, Sandra E.,Harris, Daniel P.,Heaney, Harry,Stubbs, Emma C.
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p. 2274 - 2276
(2010/07/08)
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- Transition metal alkynyl complexes by transmetallation from Au(CΞCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4)
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Facile acetylide transfer reactions take place between gold(i) complexes Au(CΞCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4) and a variety of representative inorganic and organometallic complexes MXLn
- Khairul, Wan M.,Fox, Mark A.,Zaitseva, Natasha N.,Gaudio, Maryka,Yufit, Dmitry S.,Skelton, Brian W.,White, Allan H.,Howard, Judith A. K.,Bruce, Michael I.,Low, Paul J.
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p. 610 - 620
(2009/05/06)
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- Investigation of an efficient palladium-catalyzed C(sp)-C(sp) cross-coupling reaction using phosphine-olefin ligand: Application and mechanistic aspects
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A π-acceptor phosphine-electron-deficient olefin ligand was found effective in promoting Pd-catalyzed C(sp)-C(sp) cross-coupling reactions. The new protocol realized the cross-coupling of a broad scope of terminal alkynes and haloalkynes in good to excellent yields with high selectivities. Electron-rich alkynes, which are normally difficult substrates in Glaser couplings, could be employed as either nucleophiles or electrophiles. Alkynes bearing similar substituents, such as n-C5H11CCBr and n-C4H9CCH, which usually suffer from homocoupling side reactions under Cadiot-Chodkiewicz conditions, were successfully cross-coupled in the system. Preliminary kinetic studies revealed that the reaction rate was zero-order in the concentrations of both haloalkynes and terminal alkynes and first order in the loading of Pd(dba)2 and exhibited no obvious dependence on the loading of the copper salt. Control experiments with other phosphines such as PPh3 and DPPF as the ligand were carried out. All the kinetic evidence indicated that the phosphine-olefin ligand facilitated the reductive elimination in the catalytic cycle.
- Shi, Wei,Luo, Yingdong,Luo, Xiancai,Chao, Lei,Zhang, Heng,Wang, Jian,Lei, Aiwen
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p. 14713 - 14720
(2009/02/08)
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- Combination therapy
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The present invention relates to methods of treating cancer using a combination of at least two Akt inhibitors or a compound which is an inhibitor of Akt and an inhibitor of a protein kinase, which methods comprise administering to a mammal, either sequentially in any order or simultaneously, amounts of at least two therapeutic agents selected from a group consisting of a compound(s) which are inhibitors of Akt and compound(s) which are inhibitors of protein kinases. The invention also relates to methods of preparing such compositions.
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- Synthesis and some properties of lanthanum, neodymium, and samarium tert-butoxycuprates [(ButO)5Cu2Ln]2
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Lanthanum, neodymium. and samarium tert-butoxycuprates [(ButO)5Cu2Ln]2 were synthesized in high yields by reactions of ButOCu with lanthanide metals, the halides Sml2 and LnX3 (Ln = La, Nd; X = Cl, I) and by the reaction of ButOLi with a mixture of LnCl3 and CuCl. X-Ray diffraction analysis showed that the structure of [(ButO)5Cu2Sm]2 is based on octahedra formed by four copper atoms in equatorial positions and two samarium atoms in axial positions; the copper and samarium atoms are linked by μ3-bridging ButO groups. The reactions of lanthanum tert-butoxycuprate with H2O, HCl, CpH, PhC=CH, and CO2 were studied.
- Nikitinsky,Bochkarev,Khorshev
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p. 1270 - 1274
(2007/10/03)
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