- Effect of vacuum treatment in diketopyrrolopyrrole (DPP) based copolymer with ratio controlled toluene- and benzene- functional groups for efficient organic photovoltaic cells: Morphological and electrical contribution
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Solution-processed organic bulk-heterojunction (BHJ) photovoltaic cells using random copolymeric donor materials have been extensively reported due to their suitable film-forming characteristics and phase-separated nano-morphology. Here, ratio-controlled
- Park, Soyun,Tan, Xiaofeng,Jang, Woongsik,Cho, Jae Sang,Kim, Yun-Hi,Kwon, Soon-Ki,Wang, Dong Hwan
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Read Online
- A feasible approach to obtain near-infrared (NIR) emission from binuclear platinum(II) complexes containing centrosymmetric isoquinoline ligand in PLEDs
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Organic light-emitting diodes (OLEDs) of deep-red (DR)/near-infrared (NIR) emission have become an emerging hot topic in applications for medical and night-vision devices. In this article, one novel symmetrical binuclear platinum(II) complexes as well as
- Cui, Suqian,Hao, Zhaoran,Lei, Gangtie,Liu, Yajun,Liu, Yu,Zhang, Kai,Zhu, Weiguo
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Read Online
- Alcohol-soluble conjugated oligomers as the cathode interfacial layer in polymer solar cells
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Two easily accessible fluorene-based conjugated oligo-electrolytes (COEs) FTF- and FBF-NBr have been developed as the cathode interfacial layer (CIL) in inverted type polymer solar cells (iPSCs). CILsare interpretative to improving the power conversion ef
- Kim, Youn Hwan,Marsya, Mutia Anissa,Sylvianti, Nadhila,Kim, Dong Geun,Choi, Hee Lack,Park, Chan Young,Lee, Gun Dae,Kim, Joo Hyun
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Read Online
- Palladium-Catalyzed Chemoselective Borylation of (Poly)halogenated Aryl Triflates and Their Application in Consecutive Reactions
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This study reports the palladium-catalyzed chemoselective borylation of (poly)halogenated aryl triflates with a reactivity order of C?Cl>C?OTf. A catalyst system comprising Pd(OAc)2 and SelectPhos (L1) enables a reaction with high reactivity and chemoselectivity. The consecutively chemoselective borylation reaction followed by the chemoselective intermolecular Suzuki-Miyaura reaction can be performed using a one-pot two-step approach to synthesize unsymmetrical biaryl compounds containing the triflate moiety. The reaction can be scaled up to the gram scale without diminishing the yield and chemoselectivity. (Figure presented.).
- Chen, Zicong,Ng, Shan Shan,So, Chau Ming,Yuen, On Ying
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- Unreactive C-N Bond Activation of Anilines via Photoinduced Aerobic Borylation
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Unreactive C-N bond activation of anilines was achieved by photoinduced aerobic borylation. A diverse range of tertiary and secondary anilines were converted to aryl boronate esters in moderate to good yields with wide functional group tolerance under simple and ambient photochemical conditions. This transformation achieved the direct and facile C-N bond activation of unreactive anilines, providing a convenient and practical route transforming widely available anilines into useful aryl boronate esters.
- Ji, Shuohan,Qin, Shengxiang,Yin, Chunyu,Luo, Lu,Zhang, Hua
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supporting information
p. 64 - 68
(2021/12/27)
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- Activation of Aryl Carboxylic Acids by Diboron Reagents towards Nickel-Catalyzed Direct Decarbonylative Borylation
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The Ni-catalyzed decarbonylative borylation of (hetero)aryl carboxylic acids with B2cat2 has been achieved without recourse to any additives. This Ni-catalyzed method exhibits a broad substrate scope covering poorly reactive non-ortho-substituted (hetero)aryl carboxylic acids, and tolerates diverse functional groups including some of the groups active to Ni0 catalysts. The key to achieve this decarbonylative borylation reaction is the choice of B2cat2 as a coupling partner that not only acts as a borylating reagent, but also chemoselectively activates aryl carboxylic acids towards oxidative addition of their C(acyl)?O bond to Ni0 catalyst via the formation of acyloxyboron compounds. A combination of experimental and computational studies reveals a detailed plausible mechanism for this reaction system, which involves a hitherto unknown concerted decarbonylation and reductive elimination step that generates the aryl boronic ester product. This mode of boron-promoted carboxylic acid activation is also applicable to other types of reactions.
- Deng, Xi,Guo, Jiandong,Su, Weiping,Wang, Xiaotai,Zhang, Xiaofeng
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supporting information
p. 24510 - 24518
(2021/08/12)
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- Nickel-Catalyzed Ipso-Borylation of Silyloxyarenes via C-O Bond Activation
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The conversion of silyloxyarenes to boronic acid pinacol esters via nickel catalysis is described. In contrast to other borylation protocols of inert C-O bonds, the method is competent in activating the carbon-oxygen bond of silyloxyarenes in isolated aromatic systems lacking a directing group. The catalytic functionalization of benzyl silyl ethers was also achieved under these conditions. Sequential cross-coupling reactions were achieved by leveraging the orthogonal reactivity of silyloxyarenes, which could then be functionalized subsequently.
- Pein, Wesley L.,Wiensch, Eric M.,Montgomery, John
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supporting information
(2021/06/28)
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- Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation
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Substantial effort is currently being devoted to obtaining photoredox catalysts with high redox power. Yet, it remains challenging to apply the currently established methods to the activation of bonds with high bond dissociation energy and to substrates with high reduction potentials. Herein, we introduce a novel photocatalytic strategy for the activation of inert substituted arenes for aryl borylation by using thiolate as a catalyst. This catalytic system exhibits strong reducing ability and engages non-activated Caryl–F, Caryl–X, Caryl–O, Caryl–N, and Caryl–S bonds in productive radical borylation reactions, thus expanding the available aryl radical precursor scope. Despite its high reducing power, the method has a broad substrate scope and good functional-group tolerance. Spectroscopic investigations and control experiments suggest the formation of a charge-transfer complex as the key step to activate the substrates.
- K?nig, Burkhard,Wang, Hua,Wang, Shun
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p. 1653 - 1665
(2021/06/17)
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- Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides
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Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN?-*, which can be used to activate reductively recalcitrant aryl chlorides (Ered ≈ -1.9 to -2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.
- Cao, Jilei,Tang, Xinxin,Toh, Ren Wei,Wang, Han,Wu, Jie,Wu, Xiangyang,Xu, Jinhui,Yang, Xiaona,Yeow, Edwin K. L.,Zhou, Rong
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supporting information
p. 13266 - 13273
(2021/09/07)
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- Novel compound and organic light emitting device comprising the same
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The present invention provides a novel compound and an organic light emitting device including the same.
- -
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Paragraph 0249; 0255-0258
(2021/07/27)
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- NITROGENOUS CYCLIC COMPOUND AND COLOR CHANGING FILM COMPRISING SAME
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The present specification relates to a compound containing nitrogen, and a color conversion film, a backlight unit, and a display device, including the same.
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Paragraph 0120-0121; 0261-0262
(2020/04/10)
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- A synthetic approach to dimetalated arenes using flow microreactors and the switchable application to chemoselective cross-coupling reactions
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In spite of their potential utility, the chemistry of dimetalated arenes is still in its infancy because they are extremely difficult to synthesize. We report a novel method of synthesizing arenes bearing a boryl group and a metallic substituent, such as boryl, silyl, stannyl, or zincyl groups, in an integrated flow microreactor based on the generation and reactions of aryllithiums bearing a trialkyl borate moiety. The bimetallic arenes showed a remarkable chemoselectivity in palladium-catalyzed cross-coupling reactions. The selectivity was switched by the selection of the metal species that constitutes the dimetalated arenes as well as appropriate catalysts.
- Nagaki, Aiichiro,Ashikari, Yosuke,Kawaguchi, Tomoko,Mandai, Kyoko,Aizawa, Yoko
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p. 17039 - 17047
(2020/11/10)
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- Visible Light-Induced Borylation of C-O, C-N, and C-X Bonds
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Boronic acids are centrally important functional motifs and synthetic precursors. Visible light-induced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C-O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron-rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reaction exhibits excellent functional group tolerance, as demonstrated by the borylation of a range of structurally complex substrates. Remarkably, the reaction is catalyzed by phenothiazine, a simple organic photocatalyst with MW 200 that mediates the previously unachievable visible light-induced single electron reduction of phenol derivatives with reduction potentials as negative as approximately - 3 V versus SCE by a proton-coupled electron transfer mechanism. Mechanistic studies point to the crucial role of the photocatalyst-base interaction.
- Arman, Hadi D.,Dang, Hang. T.,Haug, Graham C.,He, Ru,Jin, Shengfei,Larionov, Oleg V.,Nguyen, Viet D.,Nguyen, Vu T.,Schanze, Kirk S.
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supporting information
(2020/02/04)
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- Visible-Light-Induced Ni-Catalyzed Radical Borylation of Chloroarenes
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A highly selective and general photoinduced C-Cl borylation protocol that employs [Ni(IMes)2] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for the radical borylation of chloroarenes is reported. This photoinduced system operates with visible light (400 nm) and achieves borylation of a wide range of chloroarenes with B2pin2 at room temperature in excellent yields and with high selectivity, thereby demonstrating its broad utility and functional group tolerance. Mechanistic investigations suggest that the borylation reactions proceed via a radical process. EPR studies demonstrate that [Ni(IMes)2] undergoes very fast chlorine atom abstraction from aryl chlorides to give [NiI(IMes)2Cl] and aryl radicals. Control experiments indicate that light promotes the reaction of [NiI(IMes)2Cl] with aryl chlorides generating additional aryl radicals and [NiII(IMes)2Cl2]. The aryl radicals react with an anionic sp2-sp3 diborane [B2pin2(OMe)]- formed from B2pin2 and KOMe to yield the corresponding borylation product and the [Bpin(OMe)]?- radical anion, which reduces [NiII(IMes)2Cl2] under irradiation to regenerate [NiI(IMes)2Cl] and [Ni(IMes)2] for the next catalytic cycle.
- Tian, Ya-Ming,Guo, Xiao-Ning,Krummenacher, Ivo,Wu, Zhu,Nitsch, J?rn,Braunschweig, Holger,Radius, Udo,Marder, Todd B.
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supporting information
p. 18231 - 18242
(2020/11/02)
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- Transformations of Aryl Ketones via Ligand-Promoted C?C Bond Activation
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The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this approach is typically based on carbon–carbon cleavage triggered by ring-strain release and chelation assistance, and the products are also limited to a specific structural motif. Here we report a ligand-promoted β-carbon elimination strategy to activate the carbon–carbon bonds, which results in a range of transformations of aryl ketones, leading to useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The use of a pyridine-oxazoline ligand is crucial for this catalytic transformation. A gram-scale borylation reaction of an aryl ketone via a simple one-pot operation is reported. The potential utility of this strategy is also demonstrated by the late-stage diversification of drug molecules probenecid, adapalene, and desoxyestrone, the fragrance tonalid as well as the natural product apocynin.
- Dai, Hui-Xiong,Li, Hanyuan,Li, Ling-Jun,Liu, Qi-Sheng,Ma, Biao,Wang, Mei-Ling,Wang, Xing,Wang, Zhen-Yu,Xu, Hui
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p. 14388 - 14393
(2020/07/06)
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- Luminescent tungsten(vi) complexes as photocatalysts for light-driven C-C and C-B bond formation reactions
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The realization of photocatalysis for practical synthetic application hinges on the development of inexpensive photocatalysts which can be prepared on a large scale. Herein an air-stable, visible-light-absorbing photoluminescent tungsten(vi) complex which can be conveniently prepared at the gram-scale is described. This complex could catalyse photochemical organic transformation reactions including borylation of aryl halides, such as aryl chloride, reductive coupling of benzyl bromides for C-C bond formation, reductive coupling of phenacyl bromides, and decarboxylative coupling of redox-active esters of alkyl carboxylic acid with high product yields and broad functional group tolerance.
- Chan, Kaai-Tung,Che, Chi-Ming,Du, Lili,Liu, Yungen,Phillips, David Lee,To, Wai-Pong,Tong, Glenna So Ming,Wu, Liang-Liang,Yu, Daohong
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p. 6370 - 6382
(2020/07/15)
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- Visible-light-mediated borylation of aryl and alkyl halides with a palladium complex
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Palladium catalyzed visible-light-mediated borylation of inactivated aryl and alkyl halides is reported; the method provided high yields and excellent functional group compatibility. Furthermore, arylsilicates were synthesized selectively using dimethylphenylsilyl boronic ester via changing the reaction conditions. Finally, the possible reaction mechanism is determined through fluorescence quenching and turn on/off experiments.
- Zhao, Jia-Hui,Zhou, Zhao-Zhao,Zhang, Yue,Su, Xuan,Chen, Xi-Meng,Liang, Yong-Min
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supporting information
p. 4390 - 4394
(2020/10/20)
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- DIAMINE COMPOUND, POLYIMIDE PRECURSOR AND POLYIMIDE FILM PREPARED BY USING SAME
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The present invention discloses a novel diamine having a structure including an intramolecular imide group while having an aromatic ring group with a rigid structure. In addition, and by comprising the novel diamine as a polymerization component, the present invention can provide a polyimide film having improved mechanical and thermal properties while maintaining optical properties of polyimide.
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Paragraph 0306-0308; 0318-0320
(2020/09/26)
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- DIAMINE COMPOUND, AND POLYIMIDE PRECURSOR AND POLYIMIDE FILM PREPARED BY USING THE SAME
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The present invention disclosed a novel diamine compound including a structure in which a phenylene linker (L) connecting an intramolecular imide ring and the imide ring is bonded to a phenyl ring substituted with -NH-(C=O)- or -O-(C=O)-. A polyimide film prepared by polymerizing the novel diamine compound has not only improved mechanical and thermal properties, but also an excellent refractive index.COPYRIGHT KIPO 2021
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Paragraph 0241-0244; 0382-0385
(2020/11/03)
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- Boronate Ester-Capped Helicates
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Triple-stranded helicates were obtained by metal-templated multicomponent reactions of bispyridyloxime ligands with arylboronic acids. The helicates feature two hexa-coordinated MII ions (M=Fe, Zn, or Mn), which are embedded in a macrobicyclic ligand framework, and two arylboronate ester capping groups. The latter can be used to introduce functional groups such as pyridines, aldehydes, nitriles, and carboxylic acids in apical position. The functionalized helicates have the potential to be used as nanoscale building blocks for more complex assemblies, as evidenced by the synthesis of a 3 nm-sized trianglimine.
- Depallens, Adrien B.,Fadaei-Tirani, Farzaneh,Giraldi, Erica,Ortiz, Daniel,Scopelliti, Rosario,Severin, Kay
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supporting information
(2020/06/09)
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- Photoactive thin films of terphenylene-based amorphous polymers. Synthesis, electrooptical properties, and role of photoquenching and inner filter effects in the chemosensing of nitroaromatics
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New photoactive segmented conjugated polymers with terphenylene chromophores were synthesized, and the chemosensing abilities to detect nitroaromatics compounds (NACs) of the polymeric thin films were evaluated in aqueous media. The thin films are strongl
- Garay, Raúl O.,Del Rosso, Pablo G.,Romagnoli, Maria J.,Almassio, Marcela F.,Schvval, Ana Belén
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- Room temperature Pd(0)/Ad3P-catalyzed coupling reactions of aryl chlorides with bis(pinacolato)diboron
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Room temperature Pd(0)/Ad3P-catalyzed cross-coupling reactions of aryl chlorides with bis(pinacolato)diboron are described. The Pd(0)/Ad3P catalyst, generated from Ad3P-coordinated acetanilide-based palladacycle complex, proved to be an efficient catalyst system for the Miyaura borylation reactions of a variety of aryl chlorides with bis(pinacolato)diboron. The mild reaction condition, the easy availability of the catalyst and good coupling yields make these reactions potentially useful in organic synthesis.
- Dong, Jie,Guo, Hui,Peng, Wei,Hu, Qiao-Sheng
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supporting information
p. 760 - 763
(2019/02/16)
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- Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions
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The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (CuI/CuI*/Cu0) was suggested.
- Nitelet, Antoine,Thevenet, Damien,Schiavi, Bruno,Hardouin, Christophe,Fournier, Jean,Tamion, Rodolphe,Pannecoucke, Xavier,Jubault, Philippe,Poisson, Thomas
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supporting information
p. 3262 - 3266
(2019/02/13)
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- Mechanism and Scope of Nickel-Catalyzed Decarbonylative Borylation of Carboxylic Acid Fluorides
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This Article describes the development of a base-free, nickel-catalyzed decarbonylative coupling of carboxylic acid fluorides with diboron reagents to selectively afford aryl boronate ester products. Detailed studies were conducted to assess the relative rates of direct transmetalation between aryl boronate esters and diboron reagents and a bisphosphine nickel(aryl)(fluoride) intermediate. These investigations revealed that diboron reagents undergo transmetalation with this Ni(aryl)(fluoride) intermediate at rates significantly faster than their aryl boronate ester congeners. Furthermore, the reactivity of both boron reagents toward transmetalation is enhanced with increasing electrophilicity of the boron center. These mechanistic insights were leveraged to develop a catalytic decarbonylative borylation of acid fluorides that proved applicable to a variety of (hetero)aryl carboxylic acid fluorides as well as diverse diboron reagents. The acid fluorides can be generated in situ directly from carboxylic acids. Furthermore, the mechanistic studies directed the identification of various air-stable Ni pre-catalysts for this transformation.
- Malapit, Christian A.,Bour, James R.,Laursen, Simon R.,Sanford, Melanie S.
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supporting information
p. 17322 - 17330
(2019/11/03)
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- Visible-Light-Induced Organocatalytic Borylation of Aryl Chlorides
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The preparation of arylboronates from unactivated aryl chlorides in a transition-metal-free manner is rather challenging. There are only few examples to achieve this goal by using ultraviolet irradiation. Based on the mechanistic understanding of the diboron/methoxide/pyridine reaction system, we achieved photoactivation of the in situ generated super electron donor and developed a visible-light-induced organocatalytic method for efficient borylation of unactivated aryl chlorides.
- Zhang, Li,Jiao, Lei
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p. 9124 - 9128
(2019/06/17)
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- Hydrogenation of (Hetero)aryl Boronate Esters with a Cyclic (Alkyl)(amino)carbene–Rhodium Complex: Direct Access to cis-Substituted Borylated Cycloalkanes and Saturated Heterocycles
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We herein report the hydrogenation of substituted aryl- and heteroaryl boronate esters for the selective synthesis of cis-substituted borylated cycloalkanes and saturated heterocycles. A cyclic (alkyl)(amino)carbene-ligated rhodium complex with two dimethyl groups at the ortho-alkyl scaffold of the carbene showed high reactivity in promoting the hydrogenation, thereby enabling the hydrogenation of (hetero)arenes with retention of the synthetically valuable boronate group. This process constitutes a clean, atom-economic, as well as chemo- and stereoselective route for the generation of cis-configured, diversely substituted borylated cycloalkanes and saturated heterocycles that are usually elusive and difficult to prepare.
- Ling, Liang,He, Yuan,Zhang, Xue,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 6554 - 6558
(2019/04/17)
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- Cleavage of C(aryl)?CH3 Bonds in the Absence of Directing Groups under Transition Metal Free Conditions
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Organic chemists now can construct carbon–carbon σ-bonds selectively and sequentially, whereas methods for the selective cleavage of carbon–carbon σ-bonds, especially for unreactive hydrocarbons, remain limited. Activation by ring strain, directing groups, or in the presence of a carbonyl or a cyano group is usually required. In this work, by using a sequential strategy site-selective cleavage and borylation of C(aryl)?CH3 bonds has been developed under directing group free and transition metal free conditions. Methyl groups of various arenes are selectively cleaved and replaced by boryl groups. Mechanistic analysis suggests that it proceeds by a sequential intermolecular oxidation and coupling of a transient aryl radical, generated by radical decarboxylation, involving a pyridine-stabilized persistent boryl radical.
- Dai, Peng-Fei,Ning, Xiao-Shan,Wang, Hua,Cui, Xian-Chao,Liu, Jie,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 5392 - 5395
(2019/03/29)
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- Copper-catalysed borylation of aryl chlorides
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We report herein the first Cu-catalysed borylation of a wide range of aryl chlorides with different electronic and steric properties using a readily prepared NHC-stabilised Cu catalyst and KOtBu as the base with B2pin2 (pin = pinacolato) as the boron reagent. The aryl chlorides are converted into their corresponding arylboronic esters in good yields. The new procedure shows broad functional group tolerance, and B2neop2 (neop = neopentyl glycolato) can also be applied as the boron reagent.
- Kuehn, Laura,Huang, Mingming,Radius, Udo,Marder, Todd B.
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supporting information
p. 6601 - 6606
(2019/07/16)
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- Diverse Multi-Functionalized Oligoarenes and Heteroarenes for Porous Crystalline Materials
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A modular synthesis of multi-functionalized biphenyl, terphenyl and higher linear oligophenylene dicarboxylic acids and pyridine-terminated oligoarenes by stepwise palladium–catalyzed borylation/Suzuki–Miyaura cross-coupling reactions is described. The presence of several distinct functional groups such as azide, hydroxy, and alkyne, as well as coordinative functional end groups (carboxylic acid or pyridine) combined in a single oligoarene molecular unit at strategic positions offer an advantageous dual-utility. First, these compounds can serve as useful molecular bricks (ditopic organic linkers) in the construction of complex porous crystalline materials. Second, after the assembly into the crystalline coordination networks, orthogonal functional sites within the linker-backbone offer tremendous potential from application perspectives as they can be modified by a wide range of post-synthetic modifications including azide–alkyne click chemistry. This allows further tailoring of the supramolecular assemblies to yield novel multifunctional materials.
- Grosjean, Sylvain,Hassan, Zahid,W?ll, Christof,Br?se, Stefan
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p. 1446 - 1460
(2018/10/24)
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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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- Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides
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An efficient catalytic system based on a Co(II)-NHC precursor has been developed for the cross coupling of bis(pinacolato)diboron with aryl halides including aryl chlorides, affording the aryl boronates in good to excellent yields. A wide range of functional groups are tolerated under mild reaction conditions. The reaction shows excellent chemoselectivity for bromide over chloride. Preliminary mechanistic investigations show that the catalytic cycle may rely on a cobalt(I)-(III) redox couple.
- Verma, Piyush Kumar,Mandal, Souvik,Geetharani
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p. 4049 - 4054
(2018/05/22)
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- A Simply Synthesized, Tough Polyarylene with Transient Mechanochromic Response
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A simple and high-yielding route to tough polyarylenes of the type poly(meta,meta,para-phenylene) (PmmpP) is developed. PmmpP is tough even in its as-synthesized state which has an intermediate molar mass of Mw≈60 kg mol?1 and exhibits outstanding mechanical properties at further optimized molecular weight of Mw=96 kg mol?1, E=0.9 GPa, ?=300 %. Statistical copolymers with para,para-spiropyran (SP) are mechanochromic, and the toughness allows mechanochromism to be investigated. Strained samples instantaneously lose color upon force release. DFT calculations show this phenomenon to be caused by the PmmpP matrix that allows build-up of sufficiently large forces to be transduced to SP, and the relatively unstable corresponding merocyanine (MC) form arising from the aromatic co-monomer. MC units covalently incorporated into PmmpP show a drastically reduced half life time of 3.1 s compared to 4.5 h obtained for SP derivatives with common 6-nitro substitution.
- Kempe, Fabian,Brügner, Oliver,Buchheit, Hannah,Momm, Sarah N.,Riehle, Felix,Hameury, Sophie,Walter, Michael,Sommer, Michael
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supporting information
p. 997 - 1000
(2017/11/30)
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- Preparation method of aryl borate ester and allyl borate ester
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The invention discloses a preparation method of aryl borate ester and allyl borate ester. The method comprises the following step: under the catalytic action of pyridine or a derivative thereof, carrying out 1) or 2) to obtain substituted boric acid ester shown as a formula I-1 or a formula I-2: 1) a reaction of a halide, bi-boric acid ester and alkoxide; 2) a reaction of a halide and a bi-boric acid ester-alkoxide complex. The method is an efficient preparation method of the aryl borate ester and the allyl borate ester. In the preparation method provided by the invention, the inexpensive pyridine or the derivative thereof is taken as a catalyst instead of a transition metal catalyst, the reaction conditions are mild, the reaction yield is high, residues of trace transition metal in a boronation product are avoided, and the cost of an aryl and allyl borate ester synthesis reaction is lowered.
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Paragraph 0073-0074; 0077
(2017/07/12)
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- Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer
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We report the direct chemoselective Brown-type oxidation of aryl organoboron systems containing two oxidizable boron groups. Basic biphasic reaction conditions enable selective formation and phase transfer of a boronic acid trihydroxyboronate in the presence of boronic acid pinacol (BPin) esters, while avoiding speciation equilibria. Spectroscopic investigations validate a base-promoted phase-selective discrimination of organoboron species. This phenomenon is general across a broad range of organoboron compounds and can also be used to invert conventional protecting group strategies, enabling chemoselective oxidation of BMIDA species over normally more reactive BPin substrates. We also demonstrate the selective oxidation of diboronic acid systems with chemoselectivity predictable a priori. The utility of this method is exemplified through the development of a chemoselective oxidative nucleophile coupling.
- Molloy, John J.,Clohessy, Thomas A.,Irving, Craig,Anderson, Niall A.,Lloyd-Jones, Guy C.,Watson, Allan J. B.
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p. 1551 - 1559
(2017/02/10)
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- Radical Metal-Free Borylation of Aryl Iodides
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A simple metal-free borylation of aryl iodides mediated by a fluoride sp 2 -sp 3 diboron adduct is described. The reaction conditions are compatible with various functional groups. Electronic effects of substituents do not affect the borylation while steric hindrance does. The reaction proceeds via a radical mechanism in which pyridine serves to stabilize the boryl radicals, generated in situ.
- Pinet, Sandra,Liautard, Virginie,Debiais, Mégane,Pucheault, Mathieu
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p. 4759 - 4768
(2017/10/03)
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- Copper-Catalyzed ipso-Borylation of Fluoroarenes
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ipso-Borylation of fluoroarenes has been achieved using an air-stable copper complex as a catalyst. Mechanistic studies suggest that the reaction proceeds via an SRN1 mechanism involving a single-electron-transfer (SET) process and not via the typical SNAr mechanism. This method differs from the previously reported nickel/copper-cocatalyzed system in terms of scope of the substrate and has exhibited good scalability. Double and triple ipso-borylations of several di- and trifluoroarenes have been also achieved efficiently, enhancing the synthetic utility of this method.
- Niwa, Takashi,Ochiai, Hidenori,Hosoya, Takamitsu
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p. 4535 - 4541
(2017/07/24)
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- Palladium-Catalyzed Double Borylation of Diaryl Sulfoxides with Diboron
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Borylation of the C-S bond of diaryl sulfoxides with bis(pinacolato)diboron (B 2 pin 2) is accomplished by means of a phosphine-ligated palladium catalyst and LiN(SiMe 3) 2 as a base. Both of the aryl rings of the diaryl sulfoxides are converted into borylated products.
- Saito, Hayate,Nogi, Keisuke,Yorimitsu, Hideki
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p. 4769 - 4774
(2017/09/30)
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- Isonicotinate Ester Catalyzed Decarboxylative Borylation of (Hetero)Aryl and Alkenyl Carboxylic Acids through N-Hydroxyphthalimide Esters
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Decarboxylative borylation of aryl and alkenyl carboxylic acids with bis(pinacolato)diboron was achieved through N-hydroxyphthalimide esters using tert-butyl isonicotinate as a catalyst under base-free conditions. A variety of aryl carboxylic acids possessing different functional groups and electronic properties can be smoothly converted to aryl boronate esters, including those that are difficult to decarboxylate under transition-metal catalysis, offering a new method enabling use of carboxylic acid as building blocks in organic synthesis. Mechanistic analysis suggests the reaction proceeds through coupling of a transient aryl radical generated by radical decarboxylation with a pyridine-stabilized persistent boryl radical. Activation of redox active esters may proceed via an intramolecular single-electron-transfer (SET) process through a pyridine-diboron-phthalimide adduct and accounts for the base-free reaction conditions.
- Cheng, Wan-Min,Shang, Rui,Zhao, Bin,Xing, Wei-Long,Fu, Yao
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supporting information
p. 4291 - 4294
(2017/08/23)
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- Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature
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Despite the wide use of aryl radicals in organic synthesis, current methods to prepare them from aryl halides, carboxylic acids, boronic acids, and diazonium salts suffer from limitations. Aryl triflates, easily obtained from phenols, are promising aryl radical progenitors but remain elusive in this regard. Inspired by the single electron transfer process for aryl halides to access aryl radicals, we developed a simple and efficient protocol to convert aryl triflates to aryl radicals. Our success lies in exploiting sodium iodide as the soft electron donor assisted by light. This strategy enables the scalable synthesis of two types of important organic molecules, i.e., aryl boronates and aryl iodides, in good to high yields, with broad functional group compatibility in a transition-metal-free manner at room temperature. This protocol is anticipated to find potential applications in other aryl-radical-involved reactions by using aryl triflates as aryl radical precursors.
- Liu, Wenbo,Yang, Xiaobo,Gao, Yang,Li, Chao-Jun
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supporting information
p. 8621 - 8627
(2017/07/06)
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- Pyridine-catalyzed radical borylation of aryl halides
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A pyridine-catalyzed transition-metal-free borylation reaction of haloarenes has been developed based on the selective cross-coupling of an aryl radical and a pyridine-stabilized boryl radical. Arylboronates were produced from haloarenes under mild conditions. This borylation reaction features a broad substrate scope, operational simplicity, and gram-scale synthetic ability.
- Zhang, Li,Jiao, Lei
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supporting information
p. 607 - 610
(2017/05/15)
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- Rhodium-Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids
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Transformation of aromatic thioesters into arylboronic esters was achieved efficiently using a rhodium catalyst. The broad functional-group tolerance and mild conditions of the method have allowed for the two-step decarboxylative borylation of a wide range of aromatic carboxylic acids, including commercially available drugs.
- Ochiai, Hidenori,Uetake, Yuta,Niwa, Takashi,Hosoya, Takamitsu
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p. 2482 - 2486
(2017/02/23)
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- A containing different conjugate bridge of the binuclear platinum (II) complex near-infrared phosphorescence material synthesis and application of (by machine translation)
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The invention discloses a conjugate bridge containing different of the binuclear platinum (II) complex near-infrared phosphorescent material and its in the organic electroluminescent diode in the application. Such a binuclear platinum complex near-infrare
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Paragraph 0054; 0056-0058
(2017/12/27)
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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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- Rhodium-Catalyzed ipso-Borylation of Alkylthioarenes via C-S Bond Cleavage
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Rhodium-catalyzed transformation of alkyl aryl sulfides into arylboronic acid pinacol esters via C-S bond cleavage is reported. In combination with transition-metal-catalyzed sulfanyl group-guided regioselective C-H borylation reactions of alkylthioarenes, this method allows the synthesis of a diverse range of multisubstituted arenes.
- Uetake, Yuta,Niwa, Takashi,Hosoya, Takamitsu
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supporting information
p. 2758 - 2761
(2016/06/15)
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- Phosphine and palladium-free synthesis of aryl and alkenyl boronates: A nano-catalytic approach
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Superparamagnetic copperferrite nanoparticle is employed as an environmentally benign and efficient catalyst to affect the borylation of aryliodides yielding the corresponding arylboronates at low catalyst loading under mild reaction conditions. This protocol tolerates various substituents present in aryl iodides and also could be extended to beta bromostyrenes in the absence of phosphine and palladium.
- Mohan, Balaji,Kang, Hyuntae,Park, Kang Hyun
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- Base-Free Palladium-Catalyzed Borylation of Aryl Chlorides with Diborons
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The base-free palladium-catalyzed borylation of aryl chlorides with diborons was achieved. The base-free conditions offered acceptable functional group compatibility. Based on experimental and computational studies, it was shown that smooth boryl transfer from the diborons to the arylpalladium chloride was promoted by strong interaction between the Lewis acidic boron and the chlorine atom on palladium.
- Yamamoto, Yutaro,Matsubara, Hiroshi,Yorimitsu, Hideki,Osuka, Atsuhiro
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p. 2317 - 2320
(2016/07/28)
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- Energy Gap between the Poly-p-phenylene Bridge and Donor Groups Controls the Hole Delocalization in Donor-Bridge-Donor Wires
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Poly-p-phenylene wires are critically important as charge-transfer materials in photovoltaics. A comparative analysis of a series of poly-p-phenylene (RPPn) wires, capped with isoalkyl (iAPPn), alkoxy (ROPPn), and dialkylamino (R2NPPn) groups, shows unexpected evolution of oxidation potentials, i.e., decrease (-260 mV) for iAPPn, while increase for ROPPn (+100 mV) and R2NPPn (+350 mV) with increasing number of p-phenylenes. Moreover, redox/optical properties and DFT calculations of R2NPPn/R2NPPn+? further show that the symmetric bell-shaped hole distribution distorts and shifts toward one end of the molecule with only 4 p-phenylenes in R2NPPn+?, while shifting of the hole occurs with 6 and 8 p-phenylenes in ROPPn+? and iAPPn+?, respectively. Availability of accurate experimental data on highly electron-rich dialkylamino-capped R2NPPn together with ROPPn and iAPPn allowed us to demonstrate, using our recently developed Marcus-based multistate model (MSM), that an increase of oxidation potentials in R2NPPn arises due to an interplay between the electronic coupling (Hab) and energy difference between the end-capped groups and bridging phenylenes (Δ?). A comparison of the three series of RPPn with varied Δ? further demonstrates that decrease/increase/no change in oxidation energies of RPPn can be predicted based on the energy gap Δ? and coupling Hab, i.e., decrease if Δ? ab (i.e., iAPPn), increase if Δ? > Hab (i.e., R2NPPn), and minimal change if Δ? ≈ Hab (i.e., ROPPn). MSM also reproduces the switching of the nature of electronic transition in higher homologues of R2NPPn+? (n ≥ 4). These findings will aid in the development of improved models for charge-transfer dynamics in donor-bridge-acceptor systems.
- Wang, Denan,Talipov, Marat R.,Ivanov, Maxim V.,Rathore, Rajendra
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supporting information
p. 16337 - 16344
(2016/12/27)
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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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- METHOD FOR PREPARING AMINOARYLBORANE COMPOUNDS OR DERIVATIVES THEREOF
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The present invention provides a process for the preparation of aminoarylborane compounds and derivatives thereof comprising a step of arylation by reacting an aryl chloride with an aminoborane compound in the presence of a catalytic system.
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- Method for preparing aminoarylborane compounds or derivatives thereof
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The present invention provides a process for the preparation of aminoarylborane compounds and derivatives thereof comprising a step of arylation by reacting an aryl chloride with an aminoborane compound in the presence of a catalytic system. Typically, th
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