cas 98-80-6, Phenylboronic acid | Articles data

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Gilman,Moore
p. 3609
(1958)
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Catalytic phenylborylation reaction by iridium(0) nanoparticles produced from hydridoiridium carborane
Well-dispersed iridium(0) nanoparticles stabilized with the ionic liquid, trihexyltetradecylphosphonium methylsulfonate, [THTdP][MS], have been successfully prepared by reduction of the precursor hydridoiridium carborane, (Ph3P)2Ir(H)-(7,8-nido-C2B9H 11). The iridium nanoparticles were found to be active catalysts for arylborylation, forming boric acids. The activity of the catalyst has been investigated as a function of the activating base, and reaction conditions. The highest yield of 91% was achieved in a microwave reactor using the base, tetra-2-pyridinylpyrazine, in the presence of [THTdP][MS]. The catalytic system could be recycled at least six times with less than a 0.5% loss of activity.
Yinghuai, Zhu,Chenyan, Koh,Ang, Thiam Peng,Emi,Monalisa, Winata,Louis, Loo Kui-Jin,Hosmane, Narayan S.,Maguire, John A.
p. 5756 - 5761
(2008)
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Novel biscapped and monocapped tris(dioxime) Mn(II) complexes: X-ray crystal structure of the first cationic tris(dioxime) Mn(II) complex [Mn(CDOH)3BPh]OH (CDOH2 = 1,2-cyclohexanedione dioxime)
This report describes the synthesis and characterization of a series of novel biscapped and monocapped tris-(dioxime) Mn(II) complexes [Mn(dioxime) 3(BR)2] and [Mn(dioxime)3BR]+ (dioxime = cyclohexanedione dioxime (CDOH2) and 1,2-dimethylglyoxyl dioxime (DMGH2); R = Me, n-Bu, and Ph). All tris(dioxime) Mn(II) complexes have been characterized by elemental analysis, IR, UV/vis, cyclic voltammetry, ESI-MS, and, in the cases of [Mn(CDOH)3BPh] OH·CHCl3 and [Mn(CDO)(CDOH)2(BBu(OC 2H5))2], X-ray crystallography. It was found that biscapped Mn(II) complexes [Mn(dioxime)3(BR)2] are not stable in the presence of water and readily hydrolyze to form monocapped cationic complexes [M(dioxime)3BR]+. This instability is most likely caused by mismatch between the size of Mn(II) and the coordination cavity of the biscapped tris(dioxime) ligands. In contrast, monocapped cationic complexes [M(dioxime)3BR]+ are very stable in aqueous solution even in the presence of PDTA (1,2-diaminopropane-N,N,N′,N′- tetraacetic acid) because of the kinetic inertness imposed by the monocapped tris(dioxime) chelators that are able to completely wrap Mn(II) into their N6 coordination cavity. [Mn(CDO)3BPh]OH has a distorted trigonal prismatic coordination geometry, with the Mn(II) being bonded by six imine-N donors. The hydroxyl groups from three dioxime chelating arms form very strong intramolecular hydrogen bonds with the hydroxide counterion so that the structure of [Mn(CDOH)3BPh]OH can be considered as being the clathrochelate with the hydroxide counterion as a cap .
Hsieh, Wen-Yuan,Liu, Shuang
p. 5034 - 5043
(2006)
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Evaluation of borinic acids as new, fast hydrogen peroxide–responsive triggers
Hydrogen peroxide (H2O2) is responsible for numerous damages when overproduced, and its detection is crucial for a better understanding of H2O2-mediated signaling in physiological and pathological processes. For this purpose, various “off–on” small fluorescent probes relying on a boronate trigger have been prepared, and this design has also been involved in the development of H2O2-activated prodrugs or theranostic tools. However, this design suffers from slow kinetics, preventing activation by H2O2 with a short response time. Therefore, faster H2O2-reactive groups are awaited. To address this issue, we have successfully developed and characterized a prototypic borinic-based fluorescent probe containing a coumarin scaffold. We determined its in vitro kinetic constants toward H2O2-promoted oxidation. We measured 1.9 × 104 M-1·S-1 as a second-order rate constant, which is 10,000-fold faster than its well-established boronic counterpart (1.8 M-1·S-1). This improved reactivity was also effective in a cellular context, rendering borinic acids an advantageous trigger for H2O2-mediated release of effectors such as fluorescent moieties.
Gatin-Fraudet, Blaise,Ottenwelter, Roxane,Le Saux, Thomas,Norsikian, Stéphanie,Pucher, Mathilde,Lombès, Thomas,Baron, Aurélie,Durand, Philippe,Doisneau, Gilles,Bourdreux, Yann,Iorga, Bogdan I.,Erard, Marie,Jullien, Ludovic,Guianvarc’h, Dominique,Urban, Dominique,Vauzeilles, Boris
(2021/12/23)

Fourth subgroup metal complex with rigid annular bridging structure and application of fourth subgroup metal complex
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a fourth subgroup metal complex with a rigid annular bridging structure and an application of the fourth subgroup metal complex. The fourth subgroup metal complex provided by the invention has a structure represented by a formula (A) or a formula (B), X is halogen or alkyl; and M is titanium, zirconium or hafnium. On the basis of a non-metallocene catalyst, a bridging structure in catalyst molecules is improved and upgraded, and a brand-new metal complex with excellent catalytic performance and good high-temperature tolerance is designed; when the fourth subgroup metal complex is used as a main catalyst to catalyze olefin polymerization reaction, under the activation action of a small amount of mixed cocatalyst, the fourth subgroup metal complex can efficiently catalyze the copolymerization reaction of ethylene and alpha-olefin to obtain polyolefin with high molecular weight and high comonomer insertion rate.
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(2021/06/23)

Bimetal complex with aryloxy ether skeleton, and preparation method and application thereof
The invention provides a bimetallic complex with an aryloxy ether skeleton, and a preparation method and application of the bimetallic complex. The bimetallic complex has a structural expression as shown in the specification. A catalytic system of the bimetallic complex shows very good catalytic activity and thermal stability when being used for catalyzing olefin homopolymerization or olefin/alphaolefin copolymerization reactions, and a polymerization product generated by catalysis has relatively high molecular weight and a high alpha-olefin insertion rate and has a very good industrial application prospect.
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(2020/11/26)

Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron-Nitrogen Coordination
Boron-containing polymers have many applications resulting from their prominent properties. Organoboron species with reversible B-O bonds have been successfully employed for the fabrication of various self-healing/healable and reprocessable polymers. However, the application of the polymers containing boronic ester or boroxine linkages is limited because of their instability to water. Herein, we report the hydrolytic stability and dynamic covalent chemistry of the nitrogen-coordinating cyclic boronic diester (NCB) linkages, and a new class of vitrimers based on NCB linkages is developed through the chemical reactions of reactive hydrogen with isocyanate. Thermodynamic and kinetic studies demonstrated that NCB linkages exhibit enhanced water and heat resistance, whereas the exchange reactions between NCB linkages can take place upon heating without any catalyst. The model compounds of NCBC-X1 and NCBC-X2 containing a urethane group and urea group, respectively, also showed higher hydrolytic stability compared to that of conventional boronic esters. Polyurethane vitrimers and poly(urea-urethane) vitrimers based on NCB linkages exhibited excellent solvent resistance and mechanical properties like general thermosets, which can be repaired, reprocessed, and recycled via the transesterification of NCB linkages upon heating. Especially, vitrimers based on NCB linkages presented improved stability to water and heat compared to those through conventional boronic esters because of the existence of N → B internal coordination. We anticipate that this work will provide a new strategy for designing the next generation of sustainable materials.
Zhang, Xiaoting,Wang, Shujuan,Jiang, Zikang,Li, Yu,Jing, Xinli
p. 21852 - 21860
(2021/01/11)

Linking Molecular Behavior to Macroscopic Properties in Ideal Dynamic Covalent Networks
Dynamic covalent networks (DCvNs) are increasingly used in advanced materials design with applications ranging from recyclable thermosets to self-healing hydrogels. However, the relationship between the underlying chemistry at the junctions of DCvNs and their macroscopic properties is still not fully understood. In this work, we constructed a robust framework to predict how complex network behavior in DCvNs emerges from the chemical landscape of the dynamic chemistry at the junction. Ideal dynamic covalent boronic ester-based hydrogels were used as model DCvNs. We developed physical models that describe how viscoelastic properties, as measured by shear rheometry, are linked to the molecular behavior of the dynamic junction, quantified via fluorescence and NMR spectroscopy and DFT calculations. Additionally, shear rheometry was combined with Transition State Theory to quantify the kinetics and thermodynamics of network rearrangements, enabling a mechanistic understanding including preferred reaction pathways for dynamic covalent chemistries. We applied this approach to corroborate the "loose-bolt"postulate for the reaction mechanism in Wulff-type boronic acids. These findings, grounded in molecular principles, advance our understanding and rational design of dynamic polymer networks, improving our ability to predict, design, and leverage their unique properties for future applications.
Marco-Dufort, Bruno,Iten, Ramon,Tibbitt, Mark W.
supporting information
p. 15371 - 15385
(2020/10/20)

Erratum: Linking molecular behavior to macroscopic properties in ideal dynamic covalent networks (Journal of the American Chemical Society (2020) 142: 36 (15371-15385) DOI: 10.1021/jacs.0c06192)
The "concentration of functional groups, c,"was defined incorrectly on page S18 of the Supporting Information. The (Table Presented) correct definition is as follows: c is the concentration of functional groups of one of the two network components, assuming that both components are present in equal amounts. Therefore, in a network formed from tetrafunctional macromers (f = 4) and where the total molar concentration of macromers is [PEG], c = f [PEG]/2 = 4[PEG]/2 = 2[PEG]. In the original Supporting Information, we took c as the total concentration of functional groups in the network, resulting in c = 4[PEG]. This formula was incorrect and resulted in erroneous values for select Keq or Gp data reported in Table 1 (page 15374) and Figure 8 (page 15381). The corrected Table 1 and Figure 8 are shown below, and the SI has been corrected accordingly. In addition, some of these data that are quoted in the article should be changed as follows (with the corrected values highlighted in bold). On page 15374: "Keq,c = 37.5 when c = 0.02 M,""Keq was determined to be 540 ± 65. [?] corresponding to Gp = 10.9 ± 2.0 kPa,"and "Keq was quantified as 277 ± 37 from NMR and 323 from DFT, corresponding to Gp = 8.0 ± 0.8 and 9.0 kPa, respectively."On page 15381: "The rheometric data exhibited a similar increase in Keq from 75 at pH 6 to 10750 at pH 9 (Figure 8c)"and "At pH 9, Keq = 1126 ± 108 and 565 (from spectroscopy and rheology, respectively) and then decreased sharply at pH 10 to Keq = 112 and 120 (Figure 8e,f)."On page 15373 (in the Figure 2 caption): "Keq = 540 ± 65."'Table Presented' These corrections do not affect any of the conclusions of the article but only the exact value of select parameters. We apologize for these errors and for any inconvenience caused to the readers. ? Associated Content: ? Supporting Information The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c10406. Synthesis, sample preparation, computational and experimental methods, and model descriptions (PDF). (Figure Presented).
Iten, Ramon,Marco-Dufort, Bruno,Tibbitt, Mark W.
supporting information
p. 18730 - 18731
(2020/11/19)

Single-Crystal-to-Single-Crystal [2 + 2] Photodimerization Involving B←N Coordination with Generation of a Thiophene Host
We report on B←N coordination to support a single-crystal-to-single-crystal reaction in the solid state. A [2 + 2] photodimerization is achieved with face-to-face π-stacks of monotopic B←N adducts composed of a phenylboronic acid catechol ester and an alkene with a terminal thiophene group. The photoreaction generates a ditopic B-adduct involving a head-to-tail cyclobutane regio- and stereoselectively. The photodimerization is accompanied by an increase in the tetrahedral character of the B atom. The resulting boron enables channel confinement of chloroform upon recrystallization.
Campillo-Alvarado, Gonzalo,Li, Changan,Feng, Zhiting,Hutchins, Kristin M.,Swenson, Dale C.,H?pfl, Herbert,Morales-Rojas, Hugo,Macgillivray, Leonard R.
supporting information
p. 2197 - 2201
(2020/06/25)

Boronic, diboronic and boric acid esters of 1,8-naphthalenediol-synthesis, structure and formation of boronium salts
The 1,8-naphthalenediolate [1,8-O2C10H8] supported boronic and boric acid esters of general formula X-B(1,8-O2C10H8), where X = C6H5 (1a), C6F5 (2a), 3,4,5-F3-C6H2 (3a), 2,4,6-F3-C6H2 (4a), 2,6-F2-C6H3 (5a), 2,6-Cl2-C6H3 (6a), 2,4,6-Me3-C6H2 (7a), 2,6-(MeO)3-C6H3 (8a), Bun (9a), MeO (10a), OH (11a) and Cl (13a), were synthesized, NMR spectroscopically characterized, and the solid-state structures of 1a-5a, 8a and 10a determined by X-ray crystallography. The acceptor numbers of 1a-7a and 13a were determined and found to be similar to their catecholate analogues, R-Bcat, indicating similar Lewis acidities of these two classes of boronic acid esters. The reaction of B2(NMe2)4 with 1,8-naphthalenediol, followed by addition of HCl furnished the diboronic acid ester B2(1,8-O2C10H8)4 (16a) in ca. 70% yield. Cl-B(1,8-O2C10H8) (13a) was shown to react with OPEt3, DMAP, 1,10-phenanthroline and 2,2′-bipyridine, resp., to give the boronium salts [(Et3PO)2B(1,8-O2C10H8)]Cl (18a), [(DMAP)2B(1,8-O2C10H8)]Cl (22a), [(2,2′-bipyridine)B(1,8-O2C10H8)]Cl (23a) and [(1,10-phenanthroline)B(1,8-O2C10H8)]Cl (24a), which were characterized by NMR spectroscopy and X-ray crystallography.
Krempner, Clemens,Manankandayalage, Chamila P.,Unruh, Daniel K.
supporting information
p. 4834 - 4842
(2020/04/27)

Detection of hydrogen peroxide using dioxazaborocanes: elucidation of the sensing mechanism at the molecular level by NMR and XPS measurements
A fluorescent dioxazaborocane was synthesised and characterized, in order to study its turn-off sensing process for hydrogen peroxide detection. The exposure of the dioxazaborocane to diluted vapours of H2O2 led to a strong non reversible quenching of the fluorescence. Both NMR and XPS analyses were carried out before and after exposure of dioxazaborocane to H2O2 vapours. They unequivocally show that the boron atom is oxidised in the film with cleavage of the N-B dative bond. Identification of products such as phenol and boric acid by NMR, supported by consistent XPS data, enabled the whole reaction sequence that explains the fluorescence quenching of dioxazaborocane upon H2O2 exposure to be described accurately. Direct hydrolysis of dioxazaborocane to diol, without oxidation, was only marginally observed.
Caron, Thomas,Palmas, Pascal,Frénois, Céline,Méthivier, Christophe,Pasquinet, Eric,Pradier, Claire-Marie,Serein-Spirau, Fran?oise,Hairault, Lionel,Montméat, Pierre
p. 4114 - 4121
(2020/03/19)

Pd- And Ni-Based Systems for the Catalytic Borylation of Aryl (Pseudo)halides with B2(OH)4
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.
p. 10334 - 10349
(2020/09/18)

Virtues of Volatility: A Facile Transesterification Approach to Boronic Acids
Boronic acids are an increasingly important compound class for many applications, including C-C bond formation reactions, medicinal chemistry, and diagnostics. The deprotection of boronic ester intermediates is frequently a problematic and inefficient step in boronic acid syntheses. We describe an approach that highly facilitates this transformation by leveraging the volatility of methylboronic acid and its diol esters. The method is performed under mild conditions, provides high yields, and eliminates cumbersome and problematic purification steps.
Hinkes, Stefan P.A.,Klein, Christian D.P.
supporting information
p. 3048 - 3052
(2019/05/10)

Enantioselective Conjugate Addition of Aryl Halides and Triflates to Electron-Deficient Olefins via Nickel- And Rhodium-Catalyzed Sequential Relay Reactions
Asymmetric conjugate addition of aryl halides or aryl triflates to electron-deficient olefins was realized by sequential Miyaura borylation and Hayashi-Miyaura conjugate addition in one pot. A nickel-catalyzed borylation of aryl halides or triflates and a rhodium-chiral diene complex catalyzed enantioselective conjugate addition was executed as a pair of relay reactions as a more efficient and greener protocol.
Fan, Chenrui,Wu, Qixu,Zhu, Chengfeng,Wu, Xiang,Li, Yougui,Luo, Yunfei,He, Jian-Bo
supporting information
p. 8888 - 8892
(2019/10/14)

The preparation of pentafluorophenyldihaloboranes from pentafluorophenylmercurials C6F5HgR and BX3: the dramatic dependence of the reaction direction on the ligand R
Abstract: In search of convenient preparations of C6F5BX2 (X = Cl, Br), reactions of C6F5HgR (R = C6F5, C6H5, C2H5, Br and Cl) with BX3 were studied. Under the action of BCl3 the order of the C–Hg bond cleavage is C6F5Hg–C6H5 > C6F5–HgC2H5 > C6F5–HgC6F5 >> C6F5–HgCl. With more reactive BBr3 the sequence is C6F5Hg–C6H5 > C6F5–HgC2H5 ~ C6F5Hg–C2H5 > C6F5–HgC6F5 ≥ C6F5–HgBr. During the study we found the simple way to alkyldibromoboranes which is presented by the preparation of C2H5BBr2 from C2H5HgBr and BBr3. It is the second example of synthesis of alkylmercury derivative in an addition to the earlier reported formation of cyclopropylmercurials from di(cyclopropyl)mercury and BX3. Graphic abstract: [Figure not available: see fulltext.].
Bardin, Vadim V.,Adonin, Nicolay Yu.
p. 1523 - 1531
(2019/07/22)

The active metal sodium or lithium quenching method (by machine translation)
This invention claims an active metal sodium or [...] method. In the use of the metal sodium to participate in free radical coupling reaction or metal lithium participation when halogen lithium exchange reaction, reaction to the end of the excess active metal usually security quenching, excessive metal sodium and lithium adopts the halogenated hydrocarbon to process quenching, to avoid using traditional water or mellow quenching when the generation of hydrogen gas, operating the safety factor is increased. The method is simple in operation, the generated coupling alkane does not influence the reaction processing, is suitable for industrial scale production quenching using. (by machine translation)
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(2019/04/26)

Magnesium promoted autocatalytic dehydrogenation of amine borane complexes: A reliable, non-cryogenic, scalable access to boronic acids
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
p. 164 - 171
(2018/12/05)

Kinetics and Mechanism of the Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes
Pd-catalyzed C-C bond-forming reactions under oxidative conditions constitute a class of important and widely used synthetic protocols. This Article describes a mechanistic investigation of the arylating carbocyclization of allenynes using boronic acids and focuses on the correlation between reaction conditions and product selectivity. Isotope effects confirm that either allenic or propargylic C-H activation occurs directly after substrate binding. With an excess of H2O, a triene product is selectively formed via allenic C-H activation. The latter C-H activation was found to be turnover-limiting and the reaction zeroth order in reactants as well as the oxidant. A dominant feature is continuous catalyst activation, which was shown to occur even in the absence of substrate. Smaller amounts of H2O lead to mixtures of triene and vinylallene products, where the latter is formed via propargylic C-H activation. The formation of triene occurs only in the presence of ArB(OH)2. Vinylallene, on the other hand, was shown to be formed by consumption of (ArBO)3 as a first-order reactant. Conditions with sub-stoichiometric BF3·OEt2 gave selectively the vinylallene product, and the reaction is first order in PhB(OH)2. Both C-H activation and transmetalation influence the reaction rate. However, with electron-deficient ArB(OH)2, C-H activation is turnover-limiting. It was difficult to establish the order of transmetalation vs C-H activation with certainty, but the results suggest that BF3·OEt2 promotes an early transmetalation. The catalytically active species were found to be dependent on the reaction conditions, and H2O is a crucial parameter in the control of selectivity.
Bartholomeyzik, Teresa,Pendrill, Robert,Lihammar, Richard,Jiang, Tuo,Widmalm, G?ran,B?ckvall, Jan-E.
supporting information
p. 298 - 309
(2018/01/17)

Bench-Stable Sulfoxide-Based Boronates: Preparation and Application in a Tandem Suzuki Reaction
A set of novel aromatic and heteroaromatic bench-stable sulfoxide-based boronates was prepared. The structure of the boronates was established by means of X-ray crystallography, and the prepared boronates were successively used in Suzuki cross-coupling reactions under different conditions. We also developed a tandem Suzuki reaction so that a base is generated during the nucleophilic addition of Grignard reagents to 4-bromobenzaldehyde. The formed intermediates were smoothly coupled with the prepared boronates and the boronic acids under external base-free conditions. (Figure presented.).
?ubiňák, Marek,Eigner, Václav,Tobrman, Tomá?
p. 4604 - 4614
(2018/10/31)

Exploiting Coupling of Boronic Acids with Triols for a pH-Dependent click-Declick Chemistry
Click-like condensation of boronic acids with specifically designed triols (boronate-triol coupling) produces stable diamantane adducts in aqueous medium, which can be controllably cleaved to initial components under acidic conditions or by using boric acid as a chemical trigger. This novel click-declick strategy allows for the creation of temporary covalent connections between two or more modular units, which was demonstrated by the synthesis of new fluorophore-labeled natural molecules (peptides, steroids), supramolecular assemblies, modified polymers, boronic acid scavengers, solid-supported organocatalysts, biodegradable COF-like materials, and dynamic combinatorial libraries.
Golovanov, Ivan S.,Mazeina, Galina S.,Nelyubina, Yulia V.,Novikov, Roman A.,Mazur, Anton S.,Britvin, Sergey N.,Tartakovsky, Vladimir A.,Ioffe, Sema L.,Sukhorukov, Alexey Yu.
p. 9756 - 9773
(2018/09/06)

An efficient method for the hydrolysis of potassium organotrifluoroborates promoted by montmorillonite K10
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.
p. 1777 - 1785
(2018/09/04)

Photoinduced Miyaura Borylation by a Rare-Earth-Metal Photoreductant: The Hexachlorocerate(III) Anion
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.
supporting information
p. 10999 - 11003
(2018/07/31)

Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water
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
p. 1842 - 1851
(2018/02/23)

Borinic Acids via Direct Arylation of Amine-Borane Complexes: An Air- and Water-Stable Boron Source
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
p. 736 - 744
(2017/02/15)

Base free Suzuki acylation reactions of sodium (aryl trihydroxyborate) salts: A novel synthesis of substituted aryl ketones
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
p. 305 - 311
(2017/07/13)

Double-Stranded Helical Oligomers Covalently Bridged by Rotary Cyclic Boronate Esters
Novel double helices covalently bridged by cyclic boronate esters were synthesized from complementary dimers with an m-terphenyl backbone joined by a chiral or achiral phenylene linker bearing diethyl boronates and diols, respectively. The X-ray crystallographic analysis and variable-temperature NMR and circular dichroism measurements, along with theoretical calculations, revealed that the double helices function as a “molecular rotor” in which the cyclic boronate ester units rotate, yielding two stable rotamers at low temperatures. Moreover, our data indicates that the covalently bonded double helices can undergo a unique helix-inversion simultaneously with a rotational motion of the boronate esters.
Iida, Hiroki,Ohmura, Kenji,Noda, Ryuta,Iwahana, Soichiro,Katagiri, Hiroshi,Ousaka, Naoki,Hayashi, Taku,Hijikata, Yuh,Irle, Stephan,Yashima, Eiji
supporting information
p. 927 - 935
(2017/04/24)

Expanding Water/Base Tolerant Frustrated Lewis Pair Chemistry to Alkylamines Enables Broad Scope Reductive Aminations
Lower Lewis acidity boranes demonstrate greater tolerance to combinations of water/strong Br?nsted bases than B(C6F5)3, this enables Si?H bond activation by a frustrated Lewis pair (FLP) mechanism to proceed in the presence of H2O/alkylamines. Specifically, BPh3has improved water tolerance in the presence of alkylamines as the Br?nsted acidic adduct H2O–BPh3does not undergo irreversible deprotonation with aliphatic amines in contrast to H2O–B(C6F5)3. Therefore BPh3is a catalyst for the reductive amination of aldehydes and ketones with alkylamines using silanes as reductants. A range of amines inaccessible using B(C6F5)3as catalyst, were accessible by reductive amination catalysed by BPh3via an operationally simple methodology requiring no purification of BPh3or reagents/solvent. BPh3has a complementary reductive amination scope to B(C6F5)3with the former not an effective catalyst for the reductive amination of arylamines, while the latter is not an effective catalyst for the reductive amination of alkylamines. This disparity is due to the different pKavalues of the water–borane adducts and the greater susceptibility of BPh3species towards protodeboronation. An understanding of the deactivation processes occurring using B(C6F5)3and BPh3as reductive amination catalysts led to the identification of a third triarylborane, B(3,5-Cl2C6H3)3, that has a broader substrate scope being able to catalyse the reductive amination of both aryl and alkyl amines with carbonyls.
Fasano, Valerio,Ingleson, Michael J.
supporting information
p. 2217 - 2224
(2017/02/18)

Under the mellow promotion aromatic amine boronise produced by the reaction of an aryl boronic acid and aryl borate method
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 0025-0028

(2017/08/25)

Lipid-membrane-incorporated arylboronate esters as agents for boron neutron capture therapy
Arylboronate esters bearing methyl groups in both of their ortho positions were stably incorporated into lipid membranes at high concentrations without undergoing hydrolysis to the corresponding boronic acids. This method could be used in combination with
Ueda, Masafumi,Ashizawa, Kengo,Sugikawa, Kouta,Koumoto, Kazuya,Nagasaki, Takeshi,Ikeda, Atsushi
p. 1565 - 1569
(2017/02/23)

Nickel-Catalyzed Direct Synthesis of Aryl Olefins from Ketones and Organoboron Reagents under Neutral Conditions
Nickel-catalyzed addition of arylboron reagents to ketones results in aryl olefins directly. The neutral condition allows acidic protons of alcohols, phenols, and malonates to be present, and fragile structures are also tolerated.
Lei, Chuanhu,Yip, Yong Jie,Zhou, Jianrong Steve
supporting information
p. 6086 - 6089
(2017/05/08)

Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles
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?
supporting information
p. 2716 - 2718
(2016/06/15)

Visible-Light Photoredox Borylation of Aryl Halides and Subsequent Aerobic Oxidative Hydroxylation
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
supporting information
p. 5248 - 5251
(2016/11/02)

Spectroscopic and computational investigations of the thermodynamics of boronate ester and diazaborole self-assembly
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.
p. 969 - 980
(2016/02/18)

Scalable, Metal- and Additive-Free, Photoinduced Borylation of Haloarenes and Quaternary Arylammonium Salts
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.
supporting information
p. 2985 - 2988
(2016/03/19)

ORGANIC COMPOUND INCLUDING FUSED CORE MOIETY, ORGANIC OPTOELECTRIC DEVICE INCLUDING THE SAME AND DISPLAY
The present invention relates to: an organic compound represented by a combination of chemical formula 1 and chemical formula 2; and an organic optoelectronic device and a display device comprising the organic compound. In chemical formulas, R1 to R5, R9 to R14, X, m and n are the same as described in the specification. Good electrical properties, light emitting properties, color properties, and the like can be obtained by employing the organic compound to the organic optoelectronic device.COPYRIGHT KIPO 2016
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Paragraph 0424-0427

(2017/01/05)

Highly twisted pyrene derivatives for non-doped blue OLEDs
New highly twisted rigid blue light-emitting materials were designed, composed of pyrene with a xylene core unit and either naphthalene or phenyl end units. These blue-emitting materials were synthesized via the Suzuki cross-coupling reaction and their structures were confirmed using FT-IR, 1H NMR, 13C NMR, and mass spectroscopy. The optical, electrochemical and thermal properties of the materials were investigated. The non-coplanar structure introduced by highly twisted xylene units provides steric hindrance, resulting in very deep blue emission. The fabricated devices exhibited a maximum external quantum efficiency (EQE) of 3.69% with CIE color coordinates (x, y: 0.15, 0.06).
Lee, Sang Bong,Park, Kwang Hun,Joo, Chul Woong,Lee, Jeong-Ik,Lee, Jonghee,Kim, Yun-Hi
p. 19 - 25
(2016/01/30)

Pyrene derivatives comprising heteroaryl amine group and organic light-emitting diode including the same
The present invention relates to a pyrene derivative represented by chemical formula A, and an organic light-emitting diode including the same. In the chemical formula A, substituents Z, Ar_1, Ar_2, R_1 to R_5, connecting groups L_1 and L_2, and X, m, p and q are the same as defined in a detailed description of the present invention.COPYRIGHT KIPO 2015
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Paragraph 0331; 0386-0391

(2016/10/10)

Synthesis of B,O,N-Doped Adamantanes and Diamantanes by Condensation of Oximes with Boronic Acids
Condensation of oximes with boronic acids RB(OH)2 or B(OH)3 affords remarkably stable 2,4,10-trioxa-1,5,7-triaza-3-boroadamantanes via an unprecedented multicomponent process. The mechanism involves the reversible generation of unstable oxime cyclotrimers, which are readily intercepted by boronic acids.
Golovanov, Ivan S.,Sukhorukov, Alexey Yu.,Nelyubina, Yulia V.,Khomutova, Yulia A.,Ioffe, Sema L.,Tartakovsky, Vladimir A.
p. 6728 - 6736
(2015/10/06)

Synthesis of Borinic Acids and Borinate Adducts Using Diisopropylaminoborane
In situ formation of aryl Grignard under Barbier condition and diisopropylaminoborane as boron source allows a complete control of the addition onto the boron electrophile. Analytically pure borinic acid derivatives were produced at the gram scale without column chromatography and isolated as borinates adducts, with ethanolamine or 8-hydroxyquinoline, after workup.
Marciasini, Ludovic,Cacciuttolo, Bastien,Vaultier, Michel,Pucheault, Mathieu
supporting information
p. 3532 - 3535
(2015/07/28)

Synthesis and Suzuki Reactions of N-Heterocyclic Carbene Difluoro(aryl)-boranes
Readily available NHC-arylboranes (NHC-BH2Ar) are converted in high yield to stable NHC-difluoro(aryl)boranes (NHC-BF2Ar) by treatment with 2 equiv of 1-chloromethyl-4-fluoro-1,4-diazonia-bicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor). In turn, the NHC-difluoro(aryl)boranes participate directly in Suzuki reactions under conditions previously used for anionic trifluoroborate salts. Accordingly, NHC-difluoroboranes are a new class of stable precursors for Suzuki reactions.
Nerkar, Swapnil,Curran, Dennis P.
supporting information
p. 3394 - 3397
(2015/08/03)

β-Selective C-Arylation of Diisobutylaluminum Hydride Modified 1,6-Anhydroglucose: Synthesis of Canagliflozin without Recourse to Conventional Protecting Groups
The β-selective phenylation of benzyl and boronate protected 1,6-anhydroglucose and the direct phenylation of unprotected 1,6-anhydroglucose (10), pretreated with i-Bu2AlH, i-Bu3Al, Et3Al, Me3Al, or n-octyl3Al, with triphenylalane or aryl(chloro)alanes is reported. The utility of the unprotected version of the method is demonstrated by the synthesis of the SGLT2 inhibitor, canagliflozin (1a), from commercially available 10 in one C-C bond-forming step. This approach circumvents the need for conventional protecting groups, and therefore no formal protection and deprotection steps are required. (Chemical Presented).
Henschke, Julian P.,Lin, Chen-Wei,Wu, Ping-Yu,Tsao, Wen-Shing,Liao, Jyh-Hsiung,Chiang, Pei-Chen
supporting information
p. 5189 - 5195
(2015/05/27)

COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF
The present invention provides a novel compound capable of improving light emitting efficiency, stability and lifespan of an element, an organic electronic element using the same and an electronic device thereof.(110) Substrate(120) Positive electrode(130) Hole injection layer(140) Hole transfer layer(141) Buffer layer(150) Light emitting layer(151) Light-emitting assisting layer(160) Electron transfer layer(170) Electron injection layer(180) Negative electrodeCOPYRIGHT KIPO 2016
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Paragraph 0263-0266

(2016/10/07)

Transition-metal-free synthesis of phenanthridinones from biaryl-2-oxamic acid under radical conditions
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
supporting information
p. 346 - 349
(2015/02/19)

Lanthanide loading of luminescent multi-tridentate polymers under thermodynamic control
This work illustrates the use of basic statistical mechanics for rationalizing the loading of linear multitridentate polymers with trivalent lanthanides, Ln(III), and identifies the specific ionic sizes of europium and yttrium as promising candidates for the further design of organized heterometallic f-f′ materials. Using [Ln(hfac)3] (hfac = hexafluoroacetylacetonate) as lanthanide carriers, the thermodynamically controlled formation of Wolf type-II lanthanidopolymers [{Ln(hfac) 3}m(L4)] is modeled with the help of two simple microscopic descriptors: (i) the intrinsic affinity of Ln(III) for the tridentate binding sites fN3Ln and (ii) the intermetallic interactions δE1-2Ln,Ln operating between two occupied adjacent sites. Selective complexation modulated by anticooperative interactions favors the fixation of Eu(III) in semiorganized lanthanidopolymers [{Eu(hfac)3} m(L4)] displaying exploitable light-downshifting.
Babel, Lucille,Hoang, Thi Nhu Y.,Nozary, Homayoun,Salamanca, Jasmina,Guenee, Laure,Piguet, Claude
p. 3568 - 3578
(2014/05/06)

Synthesis, characterization, and electroluminescent properties of iridium(III) 2-phenylpyridine-type complexes containing trifluoromethyl substituents and various main-group moieties
New heteroleptic cyclometalated iridium(III) 2-phenylpyridine-type complexes with trifluoromethyl substituents and various main-group moieties were synthesized and their photophysical, electrochemical, and electroluminescent (EL) properties studied. The emission color can be tuned by a facile derivatization of the phenyl moiety of 2-phenylpyridine with various main-group moieties, and we have prepared new yellowish-green to orange triplet emitters with enhanced charge injection/charge transporting features, which can furnish attractive EL performance in phosphorescent organic light-emitting devices (OLEDs). Attempts were also made to fabricate two-color white-light OLEDs based on a combination of fluorescent blue and phosphorescent orange emitters.
Ho, Cheuk-Lam,Lam, Ching-Shan,Sun, Ning,Ma, Dongge,Liu, Li,Yu, Zhen-Qiang,Xue, Liqin,Lin, Zhenyang,Li, Hua,Lo, Yih Hsing,Wong, Wai-Yeung
p. 999 - 1014
(2014/08/18)

Hydroboration of arynes with N-heterocyclic carbene boranes
Arynes were generated in situ from ortho-silyl aryl triflates and fluoride ions in the presence of stable N-heterocyclic carbene boranes (NHC-BH3). Spontaneous hydroboration ensued to provide stable B-aryl-substituted NHC-boranes (NHC-BH2Ar). The reaction shows good scope in terms of both the NHC-borane and aryne components and provides direct access to mono-and disubstituted NHC-boranes. The formation of unusual ortho regioisomers in the hydroboration of arynes with an electron-withdrawing group supports a hydroboration process with hydride-transfer character.
Taniguchi, Tsuyoshi,Curran, Dennis P.
p. 13150 - 13154
(2015/02/19)

Methanol-promoted borylation of arylamines: A simple and green synthetic method to arylboronic acids and arylboronates
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
p. 1577 - 1584
(2014/07/08)

An easy route to (hetero)arylboronic acids
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
supporting information
p. 6608 - 6612
(2014/06/09)

Sequential one-pot access to molecular diversity through aniline aqueous borylation
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
supporting information
p. 10568 - 10580
(2015/01/08)

Iron catalysis and water: A synergy for refunctionalization of boron
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
supporting information
p. 551 - 555
(2014/03/21)

Palladium-catalyzed borylation of aryl iodides with 2,3-dihydro-1H-benzo[d] [1,3,2]diazaboroles
The palladium-catalyzed borylation of aryl iodides with 2,3-dihydro-1H-benzo[d][1,3,2]diazaboroles was achieved. The mild reaction conditions employed allowed for the inclusion of a wide variety of functional groups in aryl iodides to be tolerated. Additionally, the borylated products can be transformed into the corresponding boronic acids or their esters under acidic conditions.
Murata, Miki,Hirai, Nobuyoshi,Okuyama, Michihiro,Namikoshi, Takeshi,Watanabe, Shinji
p. 193 - 199
(2014/01/17)

Mn-catalyzed aromatic C-H alkenylation with terminal alkynes
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
p. 1264 - 1267
(2013/03/14)