- Functionalised 2,2′-bipyridine ligands for the preparation of metallostars; X-ray structures of free ligands and preparation of copper(I) and silver(I) complexes
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2,2-Bipyridine ligands bearing functionalised aryl substituents have been prepared with the aim of subsequent functionalisation and the preparation of multinuclear metallostars. The key intermediates are compounds containing 4-methoxyphenyl substituents w
- Constable, Edwin C.,Housecroft, Catherine E.,Neuburger, Markus,Poleschak, Ingo,Zehnder, Margareta
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Read Online
- An Accelerated Modular-Orthogonal Ni-Catalyzed Methodology to Symmetric and Nonsymmetric Constitutional Isomeric AB2to AB9Dendrons Exhibiting Unprecedented Self-Organizing Principles
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Five libraries of natural and synthetic phenolic acids containing five AB3, ten constitutional isomeric AB2, one AB4, and one AB5 were previously synthesized and reported by our laboratory in 5 to 11 steps. They were employed to construct seven libraries of self-assembling dendrons, by divergent generational, deconstruction, and combined approaches, enabling the discovery of a diversity of supramolecular assemblies including Frank-Kasper phases, soft quasicrystals, and complex helical organizations, some undergoing deracemization in the crystal state. However, higher substitution patterns within a single dendron were not accessible. Here we report three libraries consisting of 30 symmetric and nonsymmetric constitutional isomeric phenolic acids with unprecedented sequenced patterns, including two AB2, three AB3, eight AB4, five AB5, six AB6, three AB7, two AB8, and one AB9 synthesized by accelerated modular-orthogonal Ni-catalyzed borylation and cross-coupling. A single etherification step with 4-(n-dodecyloxy)benzyl chloride transformed all these phenolic acids, of interest also for other applications, into self-assembling dendrons. Despite this synthetic simplicity, they led to a diversity of unprecedented self-organizing principles: lamellar structures of interest for biological membrane mimics, helical columnar assemblies from rigid-solid angle dendrons forming Tobacco Mosaic Virus-like assemblies, columnar organizations from adaptable-solid angle dendrons forming disordered micellar-like nonhelical columns, columns from supramolecular spheres, five body-centered cubic phases displaying supramolecular orientational memory, rarely encountered in previous libraries forming predominantly Frank-Kasper phases, and two Frank-Kasper phases. Lessons from these self-organizing principles, discovered within a single generation of self-assembling dendrons, may help elaborate design principles for complex helical and nonhelical organizations of synthetic and biological matter.
- Daud, Hina,Hoffman, David J.,Huang, Ning,Jezorek, Ryan L.,Malineni, Jagadeesh,McClure, Emily R.,Partridge, Benjamin E.,Percec, Virgil,Peterca, Mihai,Sahoo, Dipankar,Song, Se Lin,Sung, Paul D.,Wang, Shitao,Wang, Xuefeng,Zhang, Na
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supporting information
p. 17724 - 17743
(2021/11/04)
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- Palladium-catalyzed B-diarylation of diethylaminoborane for the synthesis of diarylborinic acids
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The palladium-catalyzed synthesis of diarylborinic acid derivatives by intermolecular cross-coupling between aryl iodides and (amino)dihydrideborane is reported. The key to success of the reaction is the use of a less bulky diethylaminoborane reagent, which facilitates the second B-arylation.
- Igarashi, Takuya,Shimazumi, Ryoma,Tobisu, Mamoru
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supporting information
p. 760 - 763
(2020/07/10)
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- Pd- And Ni-Based Systems for the Catalytic Borylation of Aryl (Pseudo)halides with B2(OH)4
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Despite recent advancements in metal-catalyzed borylations of aryl (pseudo)halides, there is a continuing need to develop robust methods to access both early-stage and late-stage organoboron intermediates amendable for further functionalization. In particular, the development of general catalytic systems that operate under mild reaction conditions across a broad range of electrophilic partners remains elusive. Herein, we report the development and application of three catalytic systems (two Pd-based and one Ni-based) for the direct borylation of aryl (pseudo)halides using tetrahydroxydiboron (B2(OH)4). For the Pd-based catalyst systems, we have identified general reaction conditions that allow for the sequestration of halide ions through simple precipitation that results in catalyst loadings as low as 0.01 mol % (100 ppm) and reaction temperatures as low as room temperature. We also describe a complementary Ni-based catalyst system that employs simple unligated Ni(II) salts as an inexpensive alternative to the Pd-based systems for the borylation of aryl (pseudo)halides. Extrapolation of all three systems to a one-pot tandem borylation/Suzuki-Miyaura cross-coupling is also demonstrated on advanced intermediates and drug substances.
- Munteanu, Charissa,Spiller, Taylor E.,Qiu, Jun,Delmonte, Albert J.,Wisniewski, Steven R.,Simmons, Eric M.,Frantz, Doug E.
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p. 10334 - 10349
(2020/09/18)
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- Asymmetric 1,4-Addition of Arylboronic Acids to β,γ-Unsaturated α-Ketoesters using Heterogeneous Chiral Metal Nanoparticle Systems
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Asymmetric 1,4-addition reactions with β,γ-unsaturated α-ketoesters are valuable because the resulting chiral ketoester compounds can be converted into various useful species that are often used as chiral building blocks in drug and natural product synthesis. However, β,γ-unsaturated α-ketoesters have two reactive points in terms of nucleophilic additions, which will lead to the 1,4-adduct, the 1,2-adduct and to the combined 1,4- and 1,2-adduct. Therefore, controlling this chemoselectivity is an important factor for the development of these transformations. Here, we developed an asymmetric 1,4-addition of aryl boronic acids to β,γ-unsaturated α-ketoesters by using heterogeneous chiral rhodium nanoparticle systems with a chiral diene ligand bearing a secondary amide moiety. The newly developed polydimethylsilane-immobilized rhodium nanoparticle catalysts showed high activity, high chemoselectivity, and excellent enantioselectivity, and this is the first heterogeneous catalytic system for this asymmetric reaction. Metal nanoparticle catalysts were recovered and reused without loss of activity or leaching of metal. (Figure presented.).
- Miyamura, Hiroyuki,Yasukawa, Tomohiro,Zhu, Zhiyuan,Kobayashi, Shū
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supporting information
p. 353 - 359
(2019/12/15)
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- Transition-Metal-Free Borylation of Aryl Bromide Using a Simple Diboron Source
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In this study, we developed a simple transition-metal-free borylation reaction of aryl bromides. Bis-boronic acid (BBA), was used, and the borylation reaction was performed using a simple procedure at a mild temperature. Under mild conditions, aryl bromides were converted to arylboronic acids directly without any deprotection steps and purified by conversion to trifluoroborate salts. The functional group tolerance was considerably high. The mechanism study suggested that this borylation reaction proceeds via a radical pathway.
- Han, Min Su,Lim, Taeho,Ryoo, Jeong Yup
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p. 10966 - 10972
(2020/09/23)
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- Aryl boronic acid preparation method
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The invention belongs to the technical field of fine chemical engineering, and relates to an aryl boronic acid preparation method. In the prior art, aryl boronic acid as a novel safe and environmentally-friendly arylation reagent is widely used in scientific research and production of various fine chemicals containing aryl structures in the fields of medicines, pesticides, advanced materials and the like; and the aryl boronic acid compound preparation method reported in the disclosed literature has problems of harsh reaction conditions and high cost. A purpose of the invention is to provide amethod, wherein an aryl boron compound is formed by carrying out a reaction on a Grignard reagent and trialkyl borate under mild conditions, the composition of the aryl boron compound is converted from the main component diaryl borate into the main component aryl borate, and the aryl borate is hydrolyzed to obtain aryl boric acid, so that the preparation cost of the acyl aryl boric acid compound can be remarkably reduced, and the method has good practical application prospect.
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Paragraph 0033-0039
(2020/01/25)
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- Magnesium promoted autocatalytic dehydrogenation of amine borane complexes: A reliable, non-cryogenic, scalable access to boronic acids
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Owing to the unusual reactivity of dialkylamine-borane complexes, a methodology was developed to simply access boronic acids. The intrinsic instability of magnesium aminoborohydride was tweaked into a tandem dehydrogenation borylation sequence. Proceeding via an autocatalytic cycle, amineborane dehydrogenation was induced by a variety of Grignard reagents. Overall, addition of the organomagnesium species onto specially designed dialkylamine-borane complexes led to a variety of boronic acids in high yields. In addition, the reaction can be performed under Barbier conditions, on a large scale.
- Marciasini, Ludovic D.,Richard, Jimmy,Cacciuttolo, Bastien,Sartori, Guillaume,Birepinte, Melodie,Chabaud, Laurent,Pinet, Sandra,Pucheault, Mathieu
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p. 164 - 171
(2018/12/05)
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- Conformational restriction design of thiophene-biphenyl-DAPY HIV-1 non-nucleoside reverse transcriptase inhibitors
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Conformational restriction is a promising strategy in the development of DAPY-type non-nucleoside reverse transcriptase inhibitors (NNRTIs). Herein, eighteen thiophene-biphenyl-DAPY derivatives were designed and synthesized as potent HIV-1 NNRTIs in which halogen and methyl groups were introduced to explore the conformationally constrained effects. Molecular docking and dynamic simulation analysis indicated that substituents on different positions of the biphenyl ring induced different dihedral angles and binding conformations, further explaining their anti-viral activities. The 2′-fluoro and 3′-chloro substitutions could form electrostatic or halogen-bonding interactions with adjacent residues of the RT enzyme. The 2′-methyl group contributed to enlarge the dihedral angle of biphenyl ring and was positioned to a space-filling hydrophobic pocket. Notably, compounds 22 and 23 with two methyl groups exhibited potent biological activity against WT HIV-1-infected MT-4 cells (EC50 = 14 and 17 nM, respectively) and RT enzyme (EC50 = 27 and 42 nM, respectively). In particular, 23 exhibited much lower cytotoxicity (CC50 = 264.19 μM) and higher selectivity index (SI = 18,564) than etravirine. Taken together, a rational conformational model for further design of DAPYs is proposed, providing a new guidance for the development of NNRTIs.
- Sang, Yali,Han,Pannecouque, Christophe,De Clercq, Erik,Zhuang, Chunlin,Chen
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- Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water
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A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 h in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.
- Zernickel, Anna,Du, Weiyuan,Ghorpade, Seema A.,Sawant, Dinesh N.,Makki, Arwa A.,Sekar, Nagaiyan,Eppinger, J?rg
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p. 1842 - 1851
(2018/02/23)
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- Copper-Catalyzed Monoorganylation of Trialkyl Borates with Functionalized Organozinc Pivalates
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Organozinc pivalates, a recently developed air- and moisture-stable organozinc species, were found for the first time as excellent organometallic species in the monoorganylation of trialkyl borates whereby boronic acids were prepared in high yields. The significant advantage of organozinc pivalates over another previously employed organometallic reagents, e. g., organolithium reagents, Grignard reagents and organozinc halides, is that the generation of multiorganylation byproducts such as borinic acids and trialkylboranes were completely suppressed. Additionally, the in situ generated boronates could be directly arranged into Suzuki-Miyaura type cross-coupling reactions to produce biaryls in high yields.
- Fu, Ying,Gou, Bei-Lei,Shi, Chun-Zhao,Du, Zhengyin,Shen, Tong
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p. 4253 - 4257
(2018/09/18)
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- Additive- and Photocatalyst-Free Borylation of Arylazo Sulfones under Visible Light
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We developed a photocatalyst-free and additive-free, visible light induced borylation reaction using arylazo sulfones as starting material. This protocol shows some advantages such as mild conditions, simple equipment, and wide substrate scope, which gives a complementary protocol for the preparation of arylboronates.
- Xu, Yuliang,Yang, Xinying,Fang, Hao
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p. 12831 - 12837
(2018/10/20)
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- Photoinduced Miyaura Borylation by a Rare-Earth-Metal Photoreductant: The Hexachlorocerate(III) Anion
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The first photoinduced carbon(sp2)–heteroatom bond forming reaction by a rare-earth-metal photoreductant, a Miyaura borylation, has been achieved. This simple, scalable, and novel borylation method that makes use of the hexachlorocerate(III) anion ([CeIIICl6]3?, derived from CeCl3) has a broad substrate scope and functional-group tolerance and can be conducted at room temperature. Combined with Suzuki–Miyaura cross-coupling, the method is applicable to the synthesis of various biaryl products, including through the use of aryl chloride substrates.
- Qiao, Yusen,Yang, Qiaomu,Schelter, Eric J.
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supporting information
p. 10999 - 11003
(2018/07/31)
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- An efficient method for the hydrolysis of potassium organotrifluoroborates promoted by montmorillonite K10
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An efficient and non-expensive method for conversion of diverse potassium organotrifluoroborates to their corresponding boronic acids promoted by montmorillonite K10 using water as the reaction solvent is described. Further interconversion of potassium organotrifluoroborates to their corresponding boronic esters, via boronic acid intermediates was also successfully accomplished. The products were obtained in good yields, being the rate of hydrolysis influenced by the type of substituent present in the boronic acid.
- Silva, Renato L.,Santos, Cosme S.,Santos, Jonh A. M.,Oliveira, Roberta A.,Menezes, Paulo H.,Freitas, Juliano C. R.
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p. 1777 - 1785
(2018/09/04)
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- ORGANIC LIGHT EMITTING DEVICE
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An organic light-emitting device having high efficiency and long lifespan including: a first electrode; a second electrode facing the first electrode; and an organic layer between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2: When compounds represented by Formulae 1 and 2 are included in the emission layer, organic light-emitting devices may exhibit improved driving voltage, improved luminance, improved efficiency, and/or improved lifespans.
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Paragraph 0254-0256
(2017/05/15)
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- Synthesis and evaluation of sulfonamide derivatives as potent Human Uric Acid Transporter 1 (hURAT1) inhibitors
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This letter presents synthesis and structure-activity relationship study of sulfonamide derivatives as inhibitors of Human Uric Acid Transporter 1 (hURAT1). Among all tested sulfonamide derivatives, compounds 9b, 16i and 19b exhibited excellent inhibition activity with IC50 value of 10, 2, and 83?nM, respectively. In addition, compounds 9b and 19b demonstrated moderate PK profile in rats.
- Yang, Xintuo,Pang, Xuehai,Fan, Lei,Li, Xinghai,Chen, Yuanwei
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supporting information
p. 1919 - 1922
(2017/04/10)
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- Base free Suzuki acylation reactions of sodium (aryl trihydroxyborate) salts: A novel synthesis of substituted aryl ketones
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The first simple and efficient base free Pd(PPh3)4 catalysed synthesis of substituted aryl ketones from acyl chlorides and easily accessible sodium aryl trihydroxyborate salts in aqueous toluene is reported. The reaction conditions appeared versatile and tolerable to a variety of functional groups including, CF3, OMe, SMe, Br, NO2, F, OH and NH2 furnishing 25 examples of substituted aryl ketones in isolated yields of up to 96% in 24 h. Beside the high purity, the ease and convenience of the isolation compared to boronic acids, sodium aryl trihydroxyborate salts could be used subsequently without the addition of excess amount of an activator and are more user-friendly in terms of the use of accurate reaction stoichiometry.
- Sithebe, Siphamandla,Molefe, Patience
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p. 305 - 311
(2017/07/13)
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- Importance of 5/6-aryl substitution on the pharmacological profile of 4?-((2-propyl-1H-benzo[d]imidazol-1-yl)methyl)-[1,1?-biphenyl]-2-carboxylic acid derived PPARγ agonists
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In this structure-activity relationship study, the influence of aryl substituents at position 5 or 6 on the pharmacological profile of the partial PPARγ agonist 4‘-((2-propyl-1H-benzo[d]imidazol-1-yl)methyl)-[1,1‘-biphenyl]-2-carboxylic acid was investigated. This lead was previously identified as the essential part of telmisartan to induce PPARγ activation. Para-OCH3-phenyl substitution strongly increased potency and efficacy independent of the position. Both compounds represent full agonists because of strong hydrophobic contacts with the amino acid Phe363 in the ligand binding domain. Partial agonists with higher potency than telmisartan or the lead were obtained with OH or Cl substituents at the phenyl ring. Molecular modeling suggested additional hydrogen or halogen bonds with Phe360 located at helix 7. It is assumed that these interactions fix helix 7, thereby promoting a partial agonist conformation of the receptor. The theoretical considerations correlate very well with the results from the luciferase transactivation assay using hPPARγ-LBD as well as those from a time-resolved fluorescent resonance energy transfer (TR-FRET) assay in which the coactivator (TRAP220, PGC-1α) recruitment and corepressor (NCoR1) release pattern was investigated.
- Obermoser, Victoria,Mauersberger, Robert,Schuster, Daniela,Czifersky, Monika,Lipova, Marina,Siegl, Monika,Kintscher, Ulrich,Gust, Ronald
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supporting information
p. 590 - 603
(2016/12/09)
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- Borinic Acids via Direct Arylation of Amine-Borane Complexes: An Air- and Water-Stable Boron Source
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A synthesis of borinic acids and borinates was optimized using amine-borane complexes as a water and air insensitive borylating agent. The reaction operates under convenient conditions using a non-cryogenic temperature and with no flash chromatography, and it gives no boron impurities. The reaction proceeds through a tandem dehydrogenation-double addition mechanism.
- Richard, Jimmy,Birepinte, Mélodie,Charbonnier, Jean Baptiste,Liautard, Virginie,Pinet, Sandra,Pucheault, Mathieu
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p. 736 - 744
(2017/02/15)
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- Development of a Concise Multikilogram Synthesis of LPA-1 Antagonist BMS-986020 via a Tandem Borylation-Suzuki Procedure
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The process development for the synthesis of BMS-986020 (1) via a palladium catalyzed tandem borylation/Suzuki reaction is described. Evaluation of conditions culminated in an efficient borylation procedure using tetrahydroxydiboron followed by a tandem Suzuki reaction employing the same commercially available palladium catalyst for both steps. This methodology addressed shortcomings of early synthetic routes and was ultimately used for the multikilogram scale synthesis of the active pharmaceutical ingredient 1. Further evaluation of the borylation reaction showed useful reactivity with a range of substituted aryl bromides and iodides as coupling partners. These findings represent a practical, efficient, mild, and scalable method for borylation.
- Smith, Michael J.,Lawler, Michael J.,Kopp, Nathaniel,McLeod, Douglas D.,Davulcu, Akin H.,Lin, Dong,Katipally, Kishta,Sfouggatakis, Chris
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supporting information
p. 1859 - 1863
(2017/11/24)
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- Under the mellow promotion aromatic amine boronise produced by the reaction of an aryl boronic acid and aryl borate method
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The invention discloses a method for preparation of aryl boronic acid and aryl borate by alcohol-promoted boronation reaction of aromatic amine, the aromatic amine which is easy to get and cheap is used as a raw material, a diboron compound is used as a boron source, a nitrite is used as a diazotization reagent, and the aryl boronic acid and aryl borate are obtained by alcohol-promoted reaction at room temperature in no presence of a catalyst. The method has the advantages of simple operation, mild reaction conditions, no presence of a metal catalyst, reduction of the production cost, high product yield, tolerance to different functional groups on aryl, and a wide adaptive range.
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Paragraph 0028; 0041-0044
(2017/08/25)
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- Visible-Light Photoredox Borylation of Aryl Halides and Subsequent Aerobic Oxidative Hydroxylation
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Efficient and practical visible-light photoredox borylation of aryl halides and subsequent aerobic oxidative hydroxylation were developed. The protocols use readily available aryl halides and bis(pinacolato)diboron as the starting materials, fac-Ir(ppy)3 as the photocatalyst, and corresponding arylboronic esters and phenols were obtained in good yields. The methods show some advantages including simple equipment, mild conditions, easy operation, and wide substrate scope. Therefore, they should provide a valuable strategy for chemical transformations.
- Jiang, Min,Yang, Haijun,Fu, Hua
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supporting information
p. 5248 - 5251
(2016/11/02)
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- Efficient metal-free photochemical borylation of aryl halides under batch and continuous-flow conditions
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A rapid, chemoselective and metal-free C-B bond-forming reaction of aryl iodides and bromides in aqueous solution at low temperatures was discovered. This reaction is amenable to batch and continuous-flow conditions and shows exceptional functional group tolerance and broad substrate scope regarding both the aryl halide and the borylating reagent. Initial mechanistic experiments indicated a photolytically generated aryl radical as the key intermediate.
- Chen, Kai,Zhang, Shuai,He, Pei,Li, Pengfei
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p. 3676 - 3680
(2016/06/09)
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- Flow Chemistry on Multigram Scale: Continuous Synthesis of Boronic Acids within 1 s
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The benefits and limitations of a simple continuous flow setup for handling and performing of organolithium chemistry on the multigram scale is described. The developed metalation platform embodies a valuable complement to existing methodologies, as it combines the benefits of Flash Chemistry (chemical synthesis on a time scale of 1 s) with remarkable throughput (g/min) while mitigating the risk of blockages.
- Hafner, Andreas,Meisenbach, Mark,Sedelmeier, Joerg
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supporting information
p. 3630 - 3633
(2016/08/16)
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- FLUOROALKANE DERIVATIVE, GELATINIZER, MESOMORPHISM COMPOUND AND GELATINOUS COMPOSITION
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PROBLEM TO BE SOLVED: To provide a novel fluoroalkane derivative, a gelatinizer consisting of the compound and a gelatinous composition containing the gelatinizer and a mesomorphism compound consisting of the novel fluoroalkane derivative. SOLUTION: There is provided a fluoroalkane derivative represented by the following general formula (1). R-X-Ar1-O-R1-O-Ar2-Y (1), where Ar1 and Ar2 represent each independently a substituted or unsubstituted bivalent aromatic group having 6 to 30 core atoms, R1 represents a substituted or unsubstituted bivalent hydrocarbon group having 1 to 20 carbon atoms which may have an oxygen atom or a sulfur atom in a chain, R represents a substituted or unsubstituted monovalent hydrocarbon group having 2 to 22 carbon atoms and a perfluoroalkyl group, X represents a group represented by -S- or -SO2- and Y represents a cyano group, a nitro group, a substituted or unsubstituted monovalent alkoxyl group having 2 to 20 carbon atoms or a fluorine atom. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0084; 0086-0087
(2016/10/27)
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- Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles
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Asymmetric arylation of aldimines catalyzed by heterogeneous chiral rhodium nanoparticles has been developed. The reaction proceeded in aqueous media without significant decomposition of the imines by hydrolysis to afford chiral (diarylmethyl)amines in high yields with outstanding enantioselectivities. This catalyst system exhibited the highest turnover number (700) in heterogeneous catalysts reported to date for these reactions. The reusability of the catalyst was also demonstrated.
- Yasukawa, Tomohiro,Kuremoto, Tatsuya,Miyamura, Hiroyuki,Kobayashi, Sh?
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supporting information
p. 2716 - 2718
(2016/06/15)
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- Palladium-Catalyzed Suzuki Reactions in Water with No Added Ligand: Effects of Reaction Scale, Temperature, pH of Aqueous Phase, and Substrate Structure
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The heterogeneous palladium-catalyzed Suzuki reactions between model aryl bromides (4-bromoanisole, 4-bromoaniline, 4-amino-2-bromopyridine, and 2-bromopyridine) and phenylboronic acid have been successfully conducted in water with no added ligand at the 100 mL scale using 20-40 mmol of aryl bromide. The product yields associated with these substrates were optimized, and key reaction parameters affecting the yields were identified. The results clearly indicate that the reaction parameters necessary to achieve high yields are substrate-dependent. In addition, it is demonstrated that aqueous Suzuki reactions of substrates containing basic nitrogen centers can produce quantitative yields of desired products in the absence of added ligand.
- Li, Zhao,Gelbaum, Carol,Heaner, William L.,Fisk, Jason,Jaganathan, Arvind,Holden, Bruce,Pollet, Pamela,Liotta, Charles L.
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p. 1489 - 1499
(2016/08/30)
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- Spectroscopic and computational investigations of the thermodynamics of boronate ester and diazaborole self-assembly
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The solution phase self-assembly of boronate esters, diazaboroles, oxathiaboroles, and dithiaboroles from the condensation of arylboronic acids with aromatic diol, diamine, hydroxythiol, and dithiol compounds in chloroform has been investigated by 1H NMR spectroscopy and computational methods. Six arylboronic acids were included in the investigations with each boronic acid varying in the substituent at its 4-position. Both computational and experimental results show that the para-substituent of the arylboronic acid does not significantly influence the favorability of forming a condensation product with a given organic donor. The type of donor, however, greatly influences the favorability of self-assembly. 1H NMR spectroscopy indicates that condensation reactions between arylboronic acids and catechol to give boronate esters are the most favored thermodynamically, followed by diazaborole formation. Computational investigations support this conclusion. Neither oxathiaboroles nor dithiaboroles form spontaneously at equilibrium in chloroform at room temperature. Computational results suggest that the effect of borylation on the frontier orbitals of each donor helps to explain differences in the favorability of their condensation reactions with arylboronic acids. The results can inform the use of boronic acids as they are increasingly utilized in the dynamic self-assembly of organic materials and as components in dynamic combinatorial libraries.
- Goldberg, Alexander R.,Northrop, Brian H.
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p. 969 - 980
(2016/02/18)
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- Scalable, Metal- and Additive-Free, Photoinduced Borylation of Haloarenes and Quaternary Arylammonium Salts
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We report herein a simple, metal- and additive-free, photoinduced borylation of haloarenes, including electron-rich fluoroarenes, as well as arylammonium salts directly to boronic acids. This borylation method has a broad scope and functional group tolerance. We show that it can be further extended to boronic esters and carried out on gram scale as well as under flow conditions.
- Mfuh, Adelphe M.,Doyle, John D.,Chhetri, Bhuwan,Arman, Hadi D.,Larionov, Oleg V.
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supporting information
p. 2985 - 2988
(2016/03/19)
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- Compound containing anthracene and pyrene and preparing method and application thereof
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The invention provides a compound containing anthracene and pyrene and a preparing method and application thereof. The compound has a structure shown in formula I, wherein R1 and R3 are independently selected from substituted or unsubstituted C1-C60 alkyl groups, substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C10-C60 condensed ring groups or substituted or unsubstituted C5-C60 heterocyclic groups; R2 is selected from hydrogen, substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C5-C60 heterocyclic groups, substituted or unsubstituted C10-C60 condensed ring groups or substituted or unsubstituted C5-C60 arylamine groups; n is 0 or 1. When current density is 20 mA/cm2, the current efficiency of the compound with the structure shown in formula I is as high as 8.9 cd/A, and service life is as long as 8500 h which is much longer than that of existing electroluminescent materials.
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Paragraph 0147-0152
(2017/02/24)
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- NOVEL AROMATIC COMPOUND WITH PERFLUOROALKYL GROUPS AT BOTH ENDS
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PROBLEM TO BE SOLVED: To provide a novel compound for thickening an organic liquid by addition thereof in an extremely small amount for solation or viscous liquid formation, particularly enabling solation at high temperature. SOLUTION: There is provided a thickener comprising a compound represented by the general formula (1) in the figure, where n and m each represent an integer from 2 to 18; R1 and R3 each represent a C0-6 branched or linear alkylene group; R2 represents a C3-18 branched or linear alkylene group; and one of X1 and X2 represents a sulfonyl group and the other represents a thio group. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0053
(2016/10/08)
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- Development of an air-stable, broadly applicable nickel source for nickel-catalyzed cross-coupling
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The synthesis of NiCl(o-tolyl)(TMEDA) (3; TMEDA = tetramethylethylenediamine) and its application in coupling reactions is described. In combination with a suitable ligand, precatalyst 3 was applied to a wide range of transformations, such as Suzuki, amination, Kumada, Negishi, Heck, borylation, and reductive coupling. Yields of products obtained with 3 are equal or superior to those obtained with common Ni sources such as Ni(cod)2 (1) and NiCl2(dme) (2). Importantly, and unlike 1, complex 3 is stable for months in air as a solid, which eliminates the need for a glovebox and greatly facilitates the reaction setup. Thus, complex 3 is the first highly versatile Ni source that combines the broad applicability of 1 with the air stability of 2.
- Magano, Javier,Monfette, Sebastien
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p. 3120 - 3123
(2015/05/20)
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- Transition-metal-free synthesis of phenanthridinones from biaryl-2-oxamic acid under radical conditions
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Na2S2O8-promoted decarboxylative cyclization of biaryl-2-oxamic acid for phenanthridinones has been developed. This work illustrates the first example of intramolecular decarboxylative amidation of unactivated arene under transition-metal-free conditions. Additionally, this approach provides an efficient and economical method to access biologically interesting phenanthridinones, an important structure motif in many natural products. (Chemical Equation Presented).
- Yuan, Ming,Chen, Li,Wang, Junwei,Chen, Shenjie,Wang, Kongchao,Xue, Yongbo,Yao, Guangmin,Luo, Zengwei,Zhang, Yonghui
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supporting information
p. 346 - 349
(2015/02/19)
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- Compounds having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body
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An object of the present invention is to provide a novel concept coadsorbent that can be used instead of conventionally-used deoxycholic acid (DCA). The present invention provides a coadsorbent having hole conduction characteristics, including the compound represented by Formula 3, and provides a dye-sensitized solar cell including a light absorbing layer including the coadsorbent having hole conduction characteristics. The photocurrent and photovoltage of the dye-sensitized solar cell can be improved because it includes a light absorbing layer including the coadsorbent having hole conduction characteristics.
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Paragraph 0139; 0140; 0145; 0146
(2014/04/04)
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- Methanol-promoted borylation of arylamines: A simple and green synthetic method to arylboronic acids and arylboronates
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A Sandmeyer borylation of arylamines via a SN2Ar pathway promoted by methanol with sodium nitrite and hydrochloric acid as diazotization agent has been developed, which provide a simple and green synthetic method to arylboronic acids and arylboronates. Georg Thieme Verlag Stuttgart New York.
- Zhao, Cong-Jun,Xue, Dong,Jia, Zhi-Hui,Wang, Chao,Xiao, Jianliang
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p. 1577 - 1584
(2014/07/08)
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- An easy route to (hetero)arylboronic acids
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An unprecedented spontaneous reactivity between diazonium salts and diboronic acid has been unveiled, leading to a versatile arylboronic acid synthesis directly from (hetero)arylamines. This fast reaction (35 min overall) tolerates a wide range of functional groups and is carried out under very mild conditions. The radical nature of the reaction mechanism has been investigated.
- Erb, William,Hellal, Akila,Albini, Mathieu,Rouden, Jacques,Blanchet, Jerome
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p. 6608 - 6612
(2014/06/09)
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- Sequential one-pot access to molecular diversity through aniline aqueous borylation
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On the basis of our recently reported aniline aqueous borylation, molecular diversity was achieved in a one-pot process by combining other reactions such as esterification, Suzuki-Miyaura coupling, hydrogenolysis, or Petasis borono-Mannich.
- Erb, William,Albini, Mathieu,Rouden, Jacques,Blanchet, Jrme
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p. 10568 - 10580
(2015/01/08)
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- Iron catalysis and water: A synergy for refunctionalization of boron
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A new catalytic system has been optimized to promote the conversion of boron species into others. FeCl3 associated with imidazole and water favors boron refunctionalization under mild conditions. Georg Thieme Verlag Stuttgart New York.
- Wood, John L.,Marciasini, Ludovic D.,Vaultier, Michel,Pucheault, Mathieu
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supporting information
p. 551 - 555
(2014/03/21)
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- Micro- and mesoporous polycyanurate networks based on triangular units
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Hyper-cross-linked polycyanurate networks (CE-P1 and CE-P2) were synthesized by means of thermal self-cyclotrimerization from two triangular cyanate resin monomers 1,3,5-tri(4-cyanatophenyl)benzene and 1,3,5-tricyanatobenzene, respectively. Interestingly, it was found that CE-P1 exhibited microporous characteristics and a moderately large BET surface area. The two narrow peaks in the nonlocal density functional theory (NLDFT) curve appeared at 0.57 and 1.01 nm. In contrast, the CE-P2 sample had a small surface area and broad pore-size distribution with major pores of around 3.39 nm, which indicated a mesoporous material. The reason for this was interpreted in terms of the geometric configuration, steric hindrance, and reactivity of the cyanate monomers. The adsorptions of CO2, H2, benzene, n-hexane, and water vapors were investigated by correlating the data with the porosity parameters, chemical structure, and composition of the two networks. The results showed that the vastly distinct pore properties significantly influenced the adsorptions of gases and vapors. In particular, organic vapors such as benzene and n-hexane tended to be adsorbed on the pore surface owing to their affinity and thereby the adsorption amounts were tightly attached to the surface area of the samples. On the contrary, the hydrophobic nature of polymers made the water molecules preferentially condense within the pores so that the pore size rather than the surface area became the dominant factor influencing the adsorption of water vapor. Copyright
- Yu, Hao,Shen, Changjiang,Wang, Zhonggang
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p. 498 - 505
(2013/07/26)
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- Mn-catalyzed aromatic C-H alkenylation with terminal alkynes
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The first manganese-catalyzed aromatic C-H alkenylation with terminal alkynes is described. The procedure features an operationally simple catalyst system containing commercially available MnBr(CO)5 and dicyclohexylamine (Cy2NH). The reaction occurs readily in a highly chemo-, regio-, and stereoselective manner delivering anti-Markovnikov E-configured olefins in high yields. Experimental study and DFT calculations reveal that (1) the reaction is initiated by a C-H activation step via the cooperation of manganese and base; (2) manganacycle and alkynylmanganese species are the key reaction intermediates; and (3) the ligand-to-ligand H-transfer and alkynyl-assisted C-H activation are the key steps rendering the reaction catalytic in manganese.
- Zhou, Bingwei,Chen, Hui,Wang, Congyang
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p. 1264 - 1267
(2013/03/14)
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- Nickel-catalyzed borylation of halides and pseudohalides with tetrahydroxydiboron [B2(OH)4]
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Arylboronic acids are gaining increased importance as reagents and target structures in a variety of useful applications. Recently, the palladium-catalyzed synthesis of arylboronic acids employing the atom-economical tetrahydroxydiboron (BBA) reagent has been reported. The high cost associated with palladium, combined with several limitations of both palladium- and copper-catalyzed processes, prompted us to develop an alternative method. Thus, the nickel-catalyzed borylation of aryl and heteroaryl halides and pseudohalides using tetrahydroxydiboron (BBA) has been formulated. The reaction proved to be widely functional group tolerant and applicable to a number of heterocyclic systems. To the best of our knowledge, the examples presented here represent the only effective Ni-catalyzed Miyaura borylations conducted at room temperature.
- Molander, Gary A.,Cavalcanti, Livia N.,Garcia-Garcia, Carolina
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p. 6427 - 6439
(2013/07/26)
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- Polymerizable compound and liquid crystal composition including it
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Provided is a polymerizable compound with large solubility in a liquid crystal composition and high reactivity irradiated by ultraviolet in the longer wavelength range. Provided is a liquid crystal composition that satisfies at least one of characteristics such as high maximum temperature of a nematic phase, low minimum temperature of a nematic phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light and high stability to heat, or that is suitably balanced between at least two of the characteristics. Provided is the polymerizable compound wherein at least one of a 1,3-phenylene structure and a 2,7-fluorenediyl structure is introduced to the polymerizable compound to give stable displays by forming a polymer with a high degree of polymerization in a PSA device production process using longer wavelengths, the liquid crystal composition includes the compound, and the liquid crystal display device contains the composition.
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Page/Page column 55; 56
(2013/03/27)
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- SYNTHESIS OF BORONIC ESTERS AND BORONIC ACIDS USING GRIGNARD REAGENTS
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Boronic esters and boronic acids are synthesized at ambient temperature in an ethereal solvent by the reaction of Grignard reagents with a boron-containing substrate. The boron-containing substrate may be a boronic ester such as pinacolborane, neopentylglycolborane, or a dialkylaminoborane compound such as diisopropylaminoborane. The Grignard reagents may be preformed or generated from an alkyl, alkenyl, aryl, arylalkyl, heteroaryl, vinyl, or allyl halide compound and Mg°. When the boron-containing substrate is a boronic ester, the reactions generally proceed at room temperature without added base in about 1 to 3 hours to form a boronic ester compound. When the boron-containing substrate is a dialkylaminoborane compound, the reactions generally proceed to completion at 0°C in about 1 hour to form a boronic acid compound.
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Paragraph 0114; 0116
(2013/03/26)
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- Reaction of grignard reagents with diisopropylaminoborane. Synthesis of alkyl, aryl, heteroaryl and allyl boronic acids from organo(diisopropyl)- aminoborane by a simple hydrolysis
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Diisopropylaminoborane (BH2-N(iPr)2) is prepared by reacting lithium diisopropylaminoborohydride (iPr-LAB) with trimethylsilyl chloride (TMSCl). Aliphatic, aromatic, and heteroaromatic (diisopropylamino) boranes are readily synthesiz
- Bailey, Christopher L.,Murphy, Chris L.,Clary, Jacob W.,Eagon, Scott,Gould, Naomi,Singaram, Bakthan
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p. 331 - 341
(2013/08/23)
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- Organotrifluoroborate hydrolysis: Boronic acid release mechanism and an acid-base paradox in cross-coupling
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The hydrolysis of potassium organotrifluoroborate (RBF3K) reagents to the corresponding boronic acids (RB(OH)2) has been studied in the context of their application in Suzuki-Miyaura coupling. The "slow release" strategy in such SM couplings is only viable if there is an appropriate gearing of the hydrolysis rate of the RBF3K reagent with the rate of catalytic turnover. In such cases, the boronic acid RB(OH)2 does not substantially accumulate, thereby minimizing side reactions such as oxidative homocoupling and protodeboronation. The study reveals that the hydrolysis rates (THF, H2O, Cs2CO 3, 55 °C) depend on a number of variables, resulting in complex solvolytic profiles with some RBF3K reagents. For example, those based on p-F-phenyl, naphthyl, furyl, and benzyl moieties are found to require acid catalysis for efficient hydrolysis. This acid-base paradox assures their slow hydrolysis under basic Suzuki-Miyaura coupling conditions. However, partial phase-splitting of the THF/H2O induced by the Cs2CO 3, resulting in a lower pH in the bulk medium, causes the reaction vessel shape, material, size, and stirring rate to have a profound impact on the hydrolysis profile. In contrast, reagents bearing, for example, isopropyl, β-styryl, and anisyl moieties undergo efficient "direct" hydrolysis, resulting in fast release of the boronic acid while reagents bearing, for example, alkynyl or nitrophenyl moieties, hydrolyze extremely slowly. Analysis of B-F bond lengths (DFT) in the intermediate difluoroborane, or the Swain-Lupton resonance parameter (R) of the R group in RBF3K, allows an a priori evaluation of whether an RBF3K reagent will likely engender "fast", "slow", or "very slow" hydrolysis. An exception to this correlation was found with vinyl-BF 3K, this reagent being sufficiently hydrophilic to partition substantially into the predominantly aqueous minor biphase, where it is rapidly hydrolyzed.
- Lennox, Alastair J. J.,Lloyd-Jones, Guy C.
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supporting information; experimental part
p. 7431 - 7441
(2012/06/16)
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- Novel multifunctional organic semiconductor materials based on 4,8-substituted 1,5-naphthyridine: Synthesis, single crystal structures, opto-electrical properties and quantum chemistry calculation
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A series of 4,8-substituted 1,5-naphthyridines (1a-1h) have been successfully synthesised by a Suzuki cross-coupling between 4,8-dibromo-1,5- naphthyridine (4) and the corresponding boronic acids (2a-2h) in the presence of catalytic palladium acetate in yields of 41.4-75.8% and have ben well characterized. They are thermally robust with high phase transition temperatures (above 186 °C). Compounds 1b, 1e and 1f crystallized in the monoclinic crystal system with the space groups P21/c, P21/c and P21/n, respectively. All of them show the lowest energy absorption bands (λmaxAbs: 294-320 nm), revealing low optical band gaps (2.77-3.79 eV). These materials emit blue fluorescence with λmaxEm ranging from 434-521 nm in dilute solution in dichloromethane and 400-501 nm in the solid state. 4,8-Substituted 1,5-naphthyridines 1a-1h have estimated electron affinities (EA) of (2.38-2.72 eV) suitable for electron-transport materials and ionization potentials (IP) of 4.85-5.04 eV facilitate excellent hole-injecting/hole-transport materials properties. Quantum chemical calculations using DFT B3LYP/6-31G* showed nearly identical the lowest unoccupied molecular orbitals (LUMO) of -2.39 to -2.19 eV and the highest occupied molecular orbitals (HOMO) of -5.33 to -6.84 eV. These results demonstrate the 4,8-substituted 1,5-naphthyridines 1a-1h with a simple architecture might be promising blue-emitting (or blue-green-emitting) materials, electron-transport materials and hole-injecting/hole-transport materials for applications for developing high-efficiency OLEDs.
- Wang, Kun-Yan,Chen, Chen,Liu, Jin-Fang,Wang, Qin,Chang, Jin,Zhu, Hong-Jun,Li, Chong
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p. 6693 - 6704
(2012/09/22)
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- Microporous cyanate resins: Synthesis, porous structure, and correlations with gas and vapor adsorptions
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Three silicon and nitrogen-centered cyanate monomers tetrakis(4- cyanatophenyl)silane, tetrakis(4-cyanatobiphenyl)silane, and tris(4-cyanatobiphenyl)amine were designedand synthesized, which were then polymerized via thermal cyclotrimerization reaction to create highly porous cyanate resin networks with systematically varied nodes and linking struts. The chemical structures of monomers and polymers were confirmed by 1H NMR, FTIR, solid-state 13C CP/MAS NMR spectra, and elemental analysis. The products are amorphous with 5% weight-loss temperatures over 428 °C. The results based on N2 and CO2 adsorption isotherms show that the pores in these polymers mainly locate in the microporous region, and the BET surface areas are up to 960 m2 g-1, which is the highest value for the porous cyanate resin reported to date. The nitrogen- and oxygen-rich characteristics of cyanate resins lead to the networks strong affinity for CO2 and thereby high CO2 adsorption capacity of 11.1 wt % at 273 K and 1.0 bar. The adsorption behaviors of H 2, CO2, benzene, n-hexane, and water vapors were investigated by correlating with the chemical composition and porosity parameters of the networks as well as the physicochemical nature of adsorbates.
- Yu, Hao,Shen, Changjiang,Tian, Mengzhe,Qu, Jing,Wang, Zhonggang
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experimental part
p. 5140 - 5150
(2012/09/22)
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- The synthesis, photophysical and electrochemical properties of a series of novel 3,8,13-substituted triindole derivatives
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The synthesis and properties of a series of new 3,8,13-substituted triindole derivatives 1a-1e are reported. The 3,8,13-substituted triindoles were thermally robust with high decomposition temperatures (≥405°C) and high melt transitions (219°C-373°C). Compound 5e was crystallized in the monoclinic system with the space group P21/n. These compounds showed UV-Vis absorption (λmaxAbs) in the range of 311-345 nm in DCM solution and 371-391 nm in solid state, and fluorescence maxima (λmaxEm) in the range of 394-412 nm in DCM solution and 416-461 nm in solid state. The fluorescence quantum yields ranged from 0.27 to 0.58. The estimated electron affinities (LUMO levels) and estimated ionization potential (HOMO levels) of compounds 1a-1e are 3.54-3.71 eV and 5.12-5.48 eV, respectively. Quantum chemical calculations using DFT B3LYP/6-31G showed nearly identical LUMO (-0.72 to -1.10 eV) and HOMO (-4.65 to -4.84 eV) values. These results demonstrated that the new 3,8,13-substituted triindoles are promising thermally stable host materials for organic light-emitting diodes with reasonable hole mobility.
- Zhu, Tianhao,He, Guangke,Chang, Jin,Zhao, Dongdong,Zhu, Xiaolin,Zhu, Hongjun
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p. 679 - 688
(2012/11/07)
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- Identification and structure-activity relationships of a novel series of estrogen receptor ligands based on 7-thiabicyclo[2.2.1]hept-2-ene-7-oxide
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To develop estrogen receptor (ER) ligands having novel structures and activities, we have explored compounds in which the central hydrophobic core has a more three-dimensional topology than typically found in estrogen ligands and thus exploits the unfilled space in the ligand-binding pocket. Here, we build upon our previous investigations of 7-oxabicyclo[2.2.1]heptene core ligands, by replacing the oxygen bridge with a sulfoxide. These new 7-thiabicyclo[2.2.1] hept-2-ene-7-oxides were conveniently prepared by a Diels-Alder reaction of 3,4-diarylthiophenes with dienophiles in the presence of an oxidant and give cycloadducts with endo stereochemistry. Several new compounds demonstrated high binding affinities with excellent ERα selectivity, but unlike oxabicyclic compounds, which are transcriptional antagonists, most thiabicyclic compounds are potent, ERα-selective agonists. Modeling suggests that the gain in activity of the thiabicyclic compounds arises from their endo stereochemistry that stabilizes an active ER conformation. Further, the disposition of methyl substituents in the phenyl groups attached to the bicyclic core unit contributes to their binding affinity and subtype selectivity.
- Wang, Pengcheng,Min, Jian,Nwachukwu, Jerome C.,Cavett, Valerie,Carlson, Kathryn E.,Guo, Pu,Zhu, Manghong,Zheng, Yangfan,Dong, Chune,Katzenellenbogen, John A.,Nettles, Kendall W.,Zhou, Hai-Bing
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experimental part
p. 2324 - 2341
(2012/05/20)
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- Blue-light-emitting multifunctional triphenylamine-centered starburst quinolines: Synthesis, electrochemical and photophysical properties
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A series of triphenylamine-centered starburst quinolines (1a-1g) have been synthesized by Friedlaender condensation of the 4,4′,4′′- triacetyltriphenylamine (2) and 2-aminophenyl ketones (3a-3g) in the presence of catalytic sulfuric acid and characterized well. They are thermally robust with high glass transition temperatures (above 176.4 °C) and decomposition temperatures (above 406 °C). These compounds emit blue fluorescence with λEmmax ranging from 433 to 446 nm in dilute toluene solution and 461 to 502 nm in the solid-state and have a relatively high efficiency (Φu = 0.98-0.57). 1a-1g have estimated ionization potentials (IP) of 4.54 to 6.45 eV which are significantly near or higher than those of well-known electron transport materials (ETMs), including tris(8- hydroxyquinoline)aluminium (Alq3) (IP = 5.7-5.9 eV), and previously reported oligoquinolines (IP = 5.53-5.81 eV). Quantum chemical calculations using DFT B3LYP/6-31G* showed the highest occupied molecular orbital (HOMO) of -5.05 to -4.81 eV, which is close to the work function of indium tin oxide (ITO). These results demonstrate the potential of 1a-1g as hole-transporting/light-emitting/electron-transport materials and the host-materials of a dopant for hole-injecting for applications in organic light-emitting devices.
- Jiang, Peng,Zhao, Dong-Dong,Yang, Xiao-Li,Zhu, Xiao-Lin,Chang, Jin,Zhu, Hong-Jun
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scheme or table
p. 4704 - 4711
(2012/08/08)
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- Synthesis of phenylboronic acids in continuous flow by means of a multijet oscillating disc reactor system operating at cryogenic temperatures
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A multijet oscillating disk (MJOD) millireactor system suitable for operating at cryogenic temperatures has been developed, assembled, and investigated. This new reactor system (cryoMJOD) was realized with the purpose to prepare various phenylboronic acids in a continuous two (three)-step telescoped synthetic process at temperatures in the interval -50 to -75 °C. In this process, n-butyllithium was reacted with a phenylbromide to provide the corresponding phenyllithium derivative, whereupon a borate was added under the formation of target product phenylboronic acid in good selectivity and medium-to-good yield (50-75%). These results were competitive with results previously revealed in the literature. The residence times of the telescoped two-step process were considerably shorter compared to those of batch mode operations for the identical syntheses. The flow process was optimized by means of statistical experimental design and multivariate regression, upon which the process was utilized for the production of a series of phenylboronic acid derivatives, all in medium-to-good yield. One of the substrates, 4-methoxyphenylboronic acid, was submitted for throughput improvements, resulting in a process with capability to produce the product phenylboronic acid in a quantity of 2.0 kg × day-1.
- Sleveland, Dagfinn,Bjorsvik, Hans-Rene
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p. 1121 - 1130
(2012/08/27)
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