- Tunable Hydrogen Release from Amine–Boranes via their Insertion into Functional Polystyrenes
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Polystyrene-g-boramine random copolymers are dihydrogen reservoirs with tunable dehydrogenation temperatures, which can be adjusted by selecting the boramine content in the copolymers. They display a unique dihydrogen thermal release profile, which is a d
- Ledoux, Audrey,Brunet, Juliette,Raynaud, Jean,Lac?te, Emmanuel
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- Facile strategy to well-defined water-soluble boronic acid (Co)polymers
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A facile route to well-defined boronic acid (co)polymers from stable and easily manipulated boronic ester monomers is presented. The polymerization of 4-pinacolatoborylstyrene by reversible addition-fragmentation chain transfer (RAFT) yielded polymeric bo
- Cambre, Jennifer N.,Roy, Debashish,Gondi, Sudershan R.,Sumerlin, Brent S.
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- One-step preparation of phenyl boron-modified magnetic mesoporous silica for selective enrichment of cis-diol-containing substances
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For enrichment and separation of cis-diol-containing compounds from biomatrix, a new type of magnetic nanoparticles named MS-48-PBSC, whichwas facilely prepared in a one-step heterogeneous reaction. The morphology results demonstrated that the MS-48-PBSC
- Fu, Hua,Hu, Jing,Zhang, Min,Wang, Yuerong,Zhang, Hongyang,Hu, Ping
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- High Glass-Transition Temperature Polymer Networks Harnessing the Dynamic Ring Opening of Pinacol Boronates
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Differential scanning calorimetry of high molar mass poly(4-vinylphenylboronic acid, pinacol ester)s evidenced unusual reactive events above 120 °C, resulting in a high glass-transition temperature of 220 °C. A reversible ring-opening reactivity of pinaco
- Brunet, Juliette,Collas, Franck,Humbert, Matthieu,Perrin, Lionel,Brunel, Fabrice,Lac?te, Emmanuel,Montarnal, Damien,Raynaud, Jean
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- Functionalized styrene synthesis via palladium-catalyzed C[sbnd]C cleavage of aryl ketones
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We report herein the synthesis of functionalized styrenes via palladium-catalyzed Suzuki–Miyaura cross-coupling reaction between aryl ketone derivatives and potassium vinyltrifluoroborate. The employment of pyridine-oxazoline ligand was the key to the cleavage of unstrained C[sbnd]C bond. A variety of functional groups and biologically important moleculars were well tolerated. The orthogonal Suzuki–Miyaura coupling demonstrated the synthetic practicability.
- Zhang, Xu,Wang, Zhen-Yu,Wang, Xing,Xu, Hui,Dai, Hui-Xiong
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- Nickel-Catalyzed Reductive Cross-Coupling of Aryl Bromides with Vinyl Acetate in Dimethyl Isosorbide as a Sustainable Solvent
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A nickel-catalyzed reductive cross-coupling has been achieved using (hetero)aryl bromides and vinyl acetate as the coupling partners. This mild, applicable method provides a reliable access to a variety of vinyl arenes, heteroarenes, and benzoheterocycles, which should expand the chemical space of precursors to fine chemicals and polymers. Importantly, a sustainable solvent, dimethyl isosorbide, is used, making this protocol more attractive from the point of view of green chemistry.
- Su, Mincong,Huang, Xia,Lei, Chuanhu,Jin, Jian
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supporting information
p. 354 - 358
(2022/01/15)
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- Merging Iridium-Catalyzed C-H Borylations with Palladium-Catalyzed Cross-Couplings Using Triorganoindium Reagents
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A versatile and efficient method to prepare borylated arenes furnished with alkyl, alkenyl, alkynyl, aryl, and heteroaryl functional groups is developed by merging Ir-catalyzed C-H borylations (CHB) with a chemoselective palladium-catalyzed cross-coupling of triorganoindium reagents (Sarandeses-Sestelo coupling) with aryl halides bearing a boronic ester substituent. Using triorganoindium cross-coupling reactions to introduce unsaturated moieties enables the synthesis of borylated arenes that would be difficult to access through the direct application of the CHB methodology. The sequential double catalyzed procedure can be also performed in one vessel.
- Jayasundara, Chathurika R. K.,Gil-Negrete, José M.,Montero Bastidas, Jose R.,Chhabra, Arzoo,Martínez, M. Montserrat,Pérez Sestelo, José,Smith, Milton R.,Maleczka, Robert E.
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p. 751 - 759
(2021/12/27)
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- Transition metal-free formal hydro/deuteromethylthiolation of unactivated alkenes
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Methylthioether is involved in the methylthiotransfer process in organisms, and therefore its functionality is of paramount importance to living organisms. Several methods for the installation of the methylthio group in small molecules have been reported previously; however, procedures starting from unactivated alkenes are rare. Herein, we report a formal hydro/deuteromethylthiolation of alkenes by using dimethyl(methylthio)sulfonium trifluoromethanesulfonate as the stimulator and sodium borohydride/deuteride as the hydrogen/deuterium source. The process represents a mild, transition metal-free and methanethiol-free route towards the synthesis of methylthioethers from unactivated alkenes. This journal is
- Chen, Shuangyang,Wang, Jia,Xie, Lan-Gui
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supporting information
p. 4037 - 4042
(2021/05/19)
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- Iminyl-Radical-Promoted C-C Bond Cleavage/Heck-Like Coupling via Dual Cobaloxime and Photoredox Catalysis
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We report herein an unprecedented protocol for radical-olefin coupling of α-imino-oxy acids and alkenes for the synthesis of alkene-containing nitriles via synergistic photoredox and cobaloxime catalysis. With visible-light irradiation, the transformation
- Tu, Jia-Lin,Tang, Wan,Xu, Wei,Liu, Feng
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p. 2929 - 2940
(2021/02/06)
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- Photoinduced Hydrocarboxylation via Thiol-Catalyzed Delivery of Formate across Activated Alkenes
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Herein we disclose a new photochemical process to prepare carboxylic acids from formate salts and alkenes. This redox-neutral hydrocarboxylation proceeds in high yields across diverse functionalized alkene substrates with excellent regioselectivity. This operationally simple procedure can be readily scaled in batch at low photocatalyst loading (0.01% photocatalyst). Furthermore, this new reaction can leverage commercially available formate carbon isotologues to enable the direct synthesis of isotopically labeled carboxylic acids. Mechanistic studies support the working model involving a thiol-catalyzed radical chain process wherein the atoms from formate are delivered across the alkene substrate via CO2?- as a key reactive intermediate.
- Alektiar, Sara N.,Wickens, Zachary K.
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supporting information
p. 13022 - 13028
(2021/09/03)
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- Olefin Hydroarylation Catalyzed by a Single-Component Cobalt(-I) Complex
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A single-component Co(-I) catalyst, [(PPh3)3Co(N2)]Li(THF)3, has been developed for olefin hydroarylations with (N-aryl)aryl imine substrates. More than 40 examples were examined under mild reaction conditions to afford the desired alkyl-arene product in good to excellent yields. Catalysis occurs in a regioselective manner to afford exclusively branched products with styrene-derived substrates or linear products for aliphatic olefins. Electron-withdrawing functional groups (e.g., -F, -CF3, and -CO2Me) were tolerated under the reaction conditions.
- Suslick, Benjamin A.,Tilley, T. Don
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supporting information
p. 1495 - 1499
(2021/03/03)
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- Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
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In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
- Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
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supporting information
p. 15396 - 15405
(2021/10/12)
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- Switchable Chemoselectivity of Reactive Intermediates Formation and Their Direct Use in A Flow Microreactor
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A chemoselectivity switchable microflow reaction was developed to generate reactive and unstable intermediates. The switchable chemoselectivity of this reaction enables a selection for one of two different intermediates, an aryllithium or a benzyl lithium, at will from the same starting material. Starting from bromo-substituted styrenes, the aryllithium intermediates were converted to the substituted styrenes, whereas the benzyl lithium intermediates were engaged in an anionic polymerization. These chemoselectivity-switchable reactions can be integrated to produce polymers that cannot be formed during typical polymerization reactions.
- Ashikari, Yosuke,Tamaki, Takashi,Kawaguchi, Tomoko,Furusawa, Mai,Yonekura, Yuya,Ishikawa, Susumu,Takahashi, Yusuke,Aizawa, Yoko,Nagaki, Aiichiro
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supporting information
p. 16107 - 16111
(2021/10/12)
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- Synthesis of All-Carbon Quaternary Centers by Palladium-Catalyzed Olefin Dicarbofunctionalization
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The redox-neutral dicarbofunctionalization of tri- and tetrasubstituted olefins to form a variety of (hetero)cyclic compounds under photoinduced palladium catalysis is described. This cascade reaction process was used to couple styrenes or acryl amides with a broad range of highly decorated olefins tethered to aryl or alkyl bromides (>50 examples). This procedure enables one or two contiguous all-carbon quaternary centers to be formed in a single step. The products could be readily diversified and applied in the synthesis of a bioactive oxindole analogue.
- Koy, Maximilian,Bellotti, Peter,Katzenburg, Felix,Daniliuc, Constantin G.,Glorius, Frank
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supporting information
p. 2375 - 2379
(2020/01/24)
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- Carbosulfenylation of Alkenes with Organozinc Reagents and Dimethyl(methylthio)sulfonium Trifluoromethanesulfonate
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The electrophilic alkylthiolation of alkenes, initiated by dimethyl(methylthio)sulfonium salts and the subsequent addition of various heteronucleophilies has been well-established. Regarding the use of carbon nucleophiles, however, only carefully designed sp-type carbon sources have been successfully applied. We herein present our findings on the methylthiolation of alkenes with dimethyl(methylthio)sulfonium trifluoromethanesulfonate, followed by carbon-carbon bond formation in the presence of organozinc reagents, thus achieving a catalyst-free protocol toward to the carbosulfenylation of alkenes.
- Tang, Meizhong,Han, Shuxiong,Huang, Shenglan,Huang, Shenlin,Xie, Lan-Gui
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supporting information
p. 9729 - 9734
(2020/12/21)
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- Radical Aza-Cyclization of α-Imino-oxy Acids for Synthesis of Alkene-Containing N-Heterocycles via Dual Cobaloxime and Photoredox Catalysis
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Nitrogen-containing heterocycles are prevalent in both naturally and synthetically bioactive molecules. We report herein an unprecedented protocol for radical aza-cyclization of α-imino-oxy acids with pendant alkenes via synergistic photoredox and cobaloxime catalysis. With or without alkenes as the intermolecular cross-coupling partners, the transformation provides a variety of corresponding alkene-containing dihydropyrrole products in satisfactory yields. In the presence of external alkenes, the tandem reaction generates E-selective coupling products with excellent chemo- and stereoselectivity.
- Tu, Jia-Lin,Liu, Jia-Li,Tang, Wan,Su, Ma,Liu, Feng
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supporting information
p. 1222 - 1226
(2020/02/15)
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- Visible-Light-Induced Pd-Catalyzed Radical Strategy for Constructing C-Vinyl Glycosides
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A novel visible-light-induced palladium-catalyzed Heck reaction for bromine sugars and aryl olefins with high regio- and stereochemistry selectivity for the preparation of C-glycosyl styrene is described. This reaction takes place in one step at room temperature by using a simple and readily available starting material. This protocol can be scaled up to a wide range of glycosyl bromide donors and aryl olefin substrates. Mechanistic studies indicate that a radical addition pathway is involved.
- Li, Ming,Qiu, Yi-Feng,Wang, Cui-Tian,Li, Xue-Song,Wei, Wan-Xu,Wang, Yu-Zhao,Bao, Qiao-Fei,Ding, Ya-Nan,Shi, Wei-Yu,Liang, Yong-Min
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supporting information
p. 6288 - 6293
(2020/09/02)
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- An Interrupted Pummerer/Nickel-Catalysed Cross-Coupling Sequence
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An interrupted Pummerer/nickel-catalysed cross-coupling strategy has been developed and used in the elaboration of styrenes. The operationally simple method can be carried out as a one-pot process, involves the direct formation of stable alkenyl sulfonium salt intermediates, utilises a commercially available sulfoxide, catalyst, and ligand, operates at ambient temperature, accommodates sp-, sp2-, and sp3-hybridised organozinc coupling partners, and delivers functionalised styrene products in high yields over two steps. An interrupted Pummerer/cyclisation approach has also been used to access carbo- and heterocyclic alkenyl sulfonium salts for cross-coupling.
- Aukland, Miles H.,Talbot, Fabien J. T.,Fernández-Salas, José A.,Ball, Matthew,Pulis, Alexander P.,Procter, David J.
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supporting information
p. 9785 - 9789
(2018/07/31)
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- Irradiation-Induced Palladium-Catalyzed Decarboxylative Heck Reaction of Aliphatic N-(Acyloxy)phthalimides at Room Temperature
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It is reported that Pd(PPh3)2Cl2 in combination with 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) under irradiation of blue LEDs efficiently catalyzes a decarboxylative Heck reaction of vinyl arenes and vinyl heteroarenes with aliphatic N-(acyloxy)phthalimides at room temperature. A broad scope of secondary, tertiary, and quaternary carboxylates, including α-amino acid derived esters, can be applied as amenable substrates with high stereoselectivity. The experimental observation was explained by excitation-state reactivity of the palladium complex under irradiation to induce single-electron transfer to activate N-(acyloxy)phthalimides, and to suppress undesired β-hydride elimination of alkyl palladium intermediates.
- Wang, Guang-Zu,Shang, Rui,Fu, Yao
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supporting information
p. 888 - 891
(2018/02/10)
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- Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors
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1,2-Disubstituted alkenes such as vinyl arenes, vinyl silanes, and vinyl boronates are among the most versatile building blocks that can be found in every sector of chemical science. We herein report a noble-metal-free method of accessing such olefins through a photo-induced decarboxylative Heck-type coupling using alkyl carboxylic acids, one of the most ubiquitous building blocks, as the feedstocks. This transformation was achieved in the absence of external oxidants through the synergistic combination of an organo photo-redox catalyst and a cobaloxime catalyst, with H2 and CO2 as the only byproducts. Both control experiments and DFT calculations supported a radical-based mechanism, which eventually led to the development of a selective three-component coupling of aliphatic carboxylic acids, acrylates, and vinyl arenes. More than 90 olefins across a wide range of functionalities were effectively synthesized with this simple protocol.
- Cao, Hui,Jiang, Heming,Feng, Hongyu,Kwan, Jeric Mun Chung,Liu, Xiaogang,Wu, Jie
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supporting information
p. 16360 - 16367
(2018/11/27)
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- Markovnikov-Selective Co(I)-Catalyzed Hydroboration of Vinylarenes and Carbonyl Compounds
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An NHC-supported Co(I) catalyst has been developed for selective Markovnikov hydroboration of vinylarenes under mild reaction conditions. The hydroboration allows highly selective synthesis of a wide range of secondary and tertiary alkyl boronates in exce
- Verma, Piyush Kumar,Sethulekshmi,Geetharani
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supporting information
p. 7840 - 7845
(2019/01/04)
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- Ir-Catalyzed Intramolecular Transannulation/C(sp2)-H Amination of 1,2,3,4-Tetrazoles by Electrocyclization
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An efficient strategy for the intramolecular denitrogenative transannulation/C(sp2)-H amination of 1,2,3,4-tetrazoles bearing C8-substituted arenes, heteroarenes, and alkenes is described. The process involves the generation of the metal-nitrene intermediate from tetrazole by the combination of [CpIrCl2]2 and AgSbF6. It has been shown that the reaction proceeds via an unprecedented electrocyclization process. The method has been successfully applied for the synthesis of a diverse array of α-carbolines and 7-azaindoles.
- Das, Sandip Kumar,Roy, Satyajit,Khatua, Hillol,Chattopadhyay, Buddhadeb
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supporting information
p. 8429 - 8433
(2018/07/09)
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- Superacidic porous polymer catalyst and its application in esterification of carboxylic acid
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Two solid acid catalysts, SAC1 and SAC2, with porous structure obtained from mesoporous hard template were synthesized and characterized by Fourier transform infrared spectroscopy, acid-base titration, nitrogen adsorption/desorption, scanning electron mic
- Park, Eun Joo,Bae, Chulsung
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p. 493 - 500
(2017/02/23)
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- Irradiation-Induced Heck Reaction of Unactivated Alkyl Halides at Room Temperature
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The palladium-catalyzed Mizoroki-Heck reaction is arguably one of the most significant carbon-carbon bond-construction reactions to be discovered in the last 50 years, with a tremendous number of applications in the production of chemicals. This Nobel-Prize-winning transformation has yet to overcome the obstacle of its general application in a range of alkyl electrophiles, especially tertiary alkyl halides that possess eliminable β-hydrogen atoms. Whereas most palladium-catalyzed cross-coupling reactions utilize the ground-state reactivity of palladium complexes under thermal conditions and generally apply a single ligand system, we report that the palladium-catalyzed Heck reaction proceeds smoothly at room temperature with a variety of tertiary, secondary, and primary alkyl bromides upon irradiation with blue light-emitting diodes in the presence of a dual phosphine ligand system. We rationalize that this unprecedented transformation is achieved by utilizing the photoexcited-state reactivity of the palladium complex to enhance oxidative addition and suppress undesired β-hydride elimination.
- Wang, Guang-Zu,Shang, Rui,Cheng, Wan-Min,Fu, Yao
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supporting information
p. 18307 - 18312
(2017/12/27)
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- Evaluation of Cyclooctatetraene-Based Aliphatic Polymers as Battery Materials: Synthesis, Electrochemical, and Thermal Characterization Supported by DFT Calculations
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Organic electrode materials for rechargeable batteries are becoming a viable alternative for existing technologies. In particular, redox polymers have shown great performances. While many cathode-active derivatives are known, the development of their anode-active counterparts, required for the design of full-organic batteries, lacks behind. Here we present investigation on the suitability of cyclooctatetraene (COT)-based aliphatic polymers as anode-active battery materials, inspired by the known reversible reduction chemistry of COT at low electrochemical potential. We found that both synthesized polystyrene derivatives, side-group functionalized with COT, showed limited electrochemical reversibility of the reduction processes, whereas reductions proceeded reversibly in model compounds of these polymers. Differential scanning calorimetry measurements and density-functional theory calculations showed that this incomplete reversibility was due to cross-linking reactions occurring between COT units in the polymers. For the future of COT-based redox polymers, we propose a molecular design that prevents these cross-linking reactions.
- Speer, Martin E.,Sterzenbach, Christopher,Esser, Birgit
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p. 1274 - 1281
(2017/11/15)
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- Synthesis of 1,3-Substituted Cyclobutanes by Allenoate-Alkene [2 + 2] Cycloaddition
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A method for the [2 + 2] cycloaddition of terminal alkenes with allenoates is presented. This process allows for the rapid synthesis of 1,3-substituted cyclobutanes in high yield under simple and robust reaction conditions.
- Conner, Michael L.,Brown, M. Kevin
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p. 8050 - 8060
(2016/09/09)
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- Palladium-Catalyzed Monofluoromethylation of Arylboronic Esters with Fluoromethyl Iodide
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The first palladium-catalyzed direct monofluoromethylation of arylboronic esters to produce monofluoromethyl arenes is reported. The reaction is typically carried out at room temperature within 4 h and has a good functional group tolerance. The monofluoromethylating agent, CH2FI, was readily prepared via a halogen-exchange process.
- Hu, Jingyu,Gao, Bing,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
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supporting information
p. 3086 - 3089
(2015/06/30)
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- Boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with silylborane and an alkoxy base: expanded scope and mechanistic studies
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A transition-metal-free method has been developed for the boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with a silylborane in the presence of an alkali-metal alkoxide. The base-mediated boryl substitution of organohalides with a silylborane was recently reported to provide the corresponding borylated products in good to high yields, and exhibit good functional group compatibility and high tolerance to steric hindrance. In this study, the scope of this transformation has been extended significantly to include a wide variety of functionalized aryl-, heteroaryl- and alkenyl halides. In particular, the boryl substitution of (E)- and (Z)-alkenyl halides proceeded smoothly to afford the corresponding alkenyl boronates in good to high yields with retention of the configuration using modified reaction conditions. The results of the mechanistic studies suggest that this boryl substitution proceeds via a carbanion-mediated mechanism.
- Yamamoto, Eiji,Ukigai, Satoshi,Ito, Hajime
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p. 2943 - 2951
(2015/06/17)
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- Investigation of a lithium-halogen exchange flow process for the preparation of boronates by using a cryo-flow reactor
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Conducting low-temperature organometallic reactions under continuous flow conditions offers the potential to more accurately control exotherms and thus provide more reproducible and scalable processes. Herein, progress towards this goal with regards to the lithium-halogen exchange/borylation reaction is reported. In addition to improving the scope of substrates available on a research scale, methods to improve reaction profiles and expedite purification of the products are also described. On moving to a continuous system, thermocouple measurements have been used to track exotherms and provide a level of safety for continuous processing of organometallic reagents. The use of an in-line continuous liquid-liquid separation device to circumvent labour intensive downstream off-line processing is also reported. A cool setup: A small footprint, modular setup based around a cryo-flow reactor is reported for the preparation of gram quantities of boronic esters. With minimum alteration, including the addition of a data logger with thermocouples and a liquid-liquid separator, the same equipment can be used to scale the process, inclusive of an in-line extraction. Copyright
- Newby, James A.,Huck, Lena,Blaylock, D. Wayne,Witt, Paul M.,Ley, Steven V.,Browne, Duncan L.
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p. 263 - 271
(2014/01/17)
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- Olefin cross-metathesis/Suzuki-Miyaura reactions on vinylphenylboronic acid pinacol esters
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A series of alkenyl phenylboronic acid pinacol esters has been synthesized via an olefin cross-metathesis reaction of vinylphenylboronic acid pinacol ester derivatives. After catalytic hydrogenation, the resulting boronates were coupled via a microwave-mediated Suzuki-Miyaura reaction to afford a library of biarylethyl aryl and biarylethyl cycloalkyl derivatives. A complementary reaction sequence involved an initial Suzuki-Miyaura coupling.
- Baltus, Christine B.,Chuckowree, Irina S.,Press, Neil J.,Day, Iain J.,Coles, Simon J.,Tizzard, Graham J.,Spencer, John
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supporting information
p. 1211 - 1217
(2013/03/13)
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- Synthesis of pinacol arylboronates from aromatic amines: A metal-free transformation
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A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.
- Qiu, Di,Jin, Liang,Zheng, Zhitong,Meng, He,Mo, Fanyang,Wang, Xi,Zhang, Yan,Wang, Jianbo
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p. 1923 - 1933
(2013/03/29)
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- 2 catalyzed hydroborations of alkenes using a bulky dioxaborocine
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4,8-Di-tert-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaborocine (1) has been prepared in high yield by the addition of H3B· SMe2 to 6,6′-methylene(2-tert-butyl-4-methylphenol). Dioxaborocine 1 is a relatively stable solid that reacts with a variety of aliphatic alkenes in the presence of catalytic amounts of [Cp*IrCl 2]2 to give the terminal hydroboration products. Analogous reactions with vinylarenes, however, afford the corresponding alkenylboronate esters along with equal amounts of the hydrogenation products. Boron products have been characterized by a number of physical and analytical methods, including single-crystal X-ray diffraction studies.
- Hunter, Nicole M.,Vogels, Christopher M.,Decken, Andreas,Bell, Andrew,Westcott, Stephen A.
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experimental part
p. 408 - 413
(2011/03/21)
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- Synthesis of functional cubes from octavinylsilsesquioxane (OVS)
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Octavinylsilsesquioxane, (CH2CH)8Si8O 12, a cubic molecule with vinyl groups at each vertex, has been elaborated to give a series of potential starting materials for nanohybrid synthesis. Terminal bromophenyl gr
- Cheng, Ge,Vautravers, Nicolas R.,Morris, Russell E.,Cole-Hamilton, David J.
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body text
p. 4662 - 4667
(2009/03/12)
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- Preparation of organoboron block copolymers via ATRP of silicon and boron-functionalized monomers
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The organoboron block copolymers were fabricated by atom transfer radical polymerization (ATRP) of silicon and boron-functionalized monomer, MBpin. It was observed that the reactivity of the functionalized monomer was similar to that of styrene, though MB
- Qin, Yang,Sukul, Vishad,Pagakos, Dimitrios,Cui, Chengzhong,Jaekle, Frieder
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p. 8987 - 8990
(2008/02/01)
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- Well-defined boron-containing polymeric Lewis acids
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A general new route to well-defined polymeric Lewis acids via borylation of silylated polymers is reported. Trimethylsilylated polystyrene (PS-Si) of controlled molecular weight and low polydispersity (PDI 3 to give poly(4-dibromoborylstyrene) (PS-B), a novel soluble boron-containing polymeric Lewis acid. PS-B readily reacted with nucleophiles serving as a precursor to a family of new polymers with boron centers of variable Lewis acidity. Reaction of PS-B with Cu(C6F5) gave the highly Lewis acidic polymer poly[4-bis(pentafluorophenyl)borylstyrene], the first polymeric analogue of tris(pentafluorophenyl)borane. Copyright
- Qin, Yang,Cheng, Guanglou,Sundararaman, Anand,Jaekle, Frieder
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p. 12672 - 12673
(2007/10/03)
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