- Unreactive C-N Bond Activation of Anilines via Photoinduced Aerobic Borylation
-
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
-
supporting information
p. 64 - 68
(2021/12/27)
-
- Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
-
In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
- Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
-
supporting information
p. 15396 - 15405
(2021/10/12)
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- Synthesis of arylboronates via the Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates with bis(pinacolato)diboron
-
The desulfitative borylation reaction of sodium arylsulfinates with bis(pinacolato)diboron or bis(neopentylglycolato)diboron under palladium catalysis has been developed, allowing selective C-B bond formation to give arylboronates with a range of functional groups in moderate to good yields under mild reaction conditions. A gram-scale preparation as well as the cascade Suzuki-Miyaura cross-coupling of arylboronates demonstrated the potential practical utility in organic synthesis.
- Qiu, Di,Li, Songyi,Yue, Guanglu,Mao, Jinshan,Xu, Bei,Yuan, Xinyu,Ye, Fei
-
-
- A compound. Electron transport material and organic electroluminescent device
-
The present application provides a compound of formula (I), which may be used in an electron transport material. The compound has the parent structure of electrosorption fragment biphenanthroline, has high bond energy among atoms, has good thermal stability, is favorable for solid accumulation of molecules, has strong electronic transition capability, can effectively reduce the driving voltage of an organic electroluminescent device, improves the current efficiency and prolongs the service life. The invention further provides an organic electroluminescent device comprising the compound of the general formula (I) and a display device.
- -
-
Paragraph 0118-0119; 0123; 0128-0129; 0132
(2021/09/01)
-
- Evaluation of the role of graphene-based Cu(i) catalysts in borylation reactions
-
Carbon-supported catalysts have been considered as macromolecular ligands which modulate the activity of the metallic catalytic center. Understanding the properties and the factors that control the interactions between the metal and support allows a fine tuning of the catalyzed processes. Although huge effort has been devoted to comprehending binding energies and charge transfer for single atom noble metals, the interaction of graphenic surfaces with cheap and versatile Cu(i) salts has been scarcely studied. A methodical experimental and theoretical analysis of different carbon-based Cu(i) materials in the context of the development of an efficient, general, scalable, and sustainable borylation reaction of aliphatic and aromatic halides has been performed. We have also examined the effect of microwave (MW) radiation in the preparation of these type of materials using sustainable graphite nanoplatelets (GNP) as a support. A detailed analysis of all the possible species in solution revealed that the catalysis is mainly due to an interesting synergetic Cu2O/graphene performance, which has been corroborated by an extensive theoretical study. We demonstrated through DFT calculations at a high level of theory that graphene enhances the reactivity of the metal in Cu2O against the halide derivative favoring a radical departure from the halogen. Moreover, this material is able to stabilize radical intermediates providing unexpected pathways not observed using homogeneous Cu(i) catalysed reactions. Finally, we proved that other common carbon-based supports like carbon black, graphene oxide and reduced graphene oxide provided poorer results in the borylation process.
- Cid, M. B.,Díaz, Cristina,Franco, Mario,Lamsabhi, Al Mokhtar,Sainz, Raquel,Tortosa, Mariola
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p. 3501 - 3513
(2021/06/06)
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- Engaging Ag(0) single atoms in silver(I) salts-mediated C-B and C-S coupling under visible light irradiation
-
Silver(I) salts were found active in the borylation and sulfenylation of aryl iodides under visible light irradiation. The optimized borylation protocol using AgF did not need any additive, operated under very mild conditions, and well tolerated a broad scope of substrates and boron sources. Formation of Ag(0) single atoms (AgSAs) during the borylation reactions was examined using high-angle annular dark field aberration-corrected scanning transmission electron microscope (HAADF AC-STEM) and electron paramagnetic resonance (EPR). The activities of the silver(I) salts were affected by the anions and could be associated with their abilities in formation of AgSAs during the reactions. Kinetic studies showed that the deiodination rate was linearly correlated with the loading of AgSAs, and hence AgSAs were the true catalytic centers for the 1e?-reduction of the C-I moieties. The oxidation state of AgSAs kept 0 in both the resting and the working states. A “work-in-tandem” mechanism involving AgSAs as the catalytic centers and AgNPs as the light absorber to achieve the borylation of aryl iodides under visible light irradiation is proposed. The current approach not only provides an alternative system for borylation and sulfenylation of aryl iodides, but also reveals a new activity of silver(I) salts involving AgSAs under visible light irradiation.
- Cui, Enxin,Guo, Lirong,Li, Haibin,Qiao, Dan,Tung, Chen-Ho,Wang, Yifeng
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p. 255 - 263
(2021/09/06)
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- Zinc Complexes with an Ethylene-Bridged Bis(β-diketiminate) Ligand: Syntheses, Structures, and Applications as Catalysts in the Borylation of Aryl Iodides
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A dinucleating bis(β-diketiminate) ligand with a flexible bridge has been employed to synthesize zinc complexes. The ligand, abbreviated H2L (H2L = N-(4-((2-((4-((2,6-diisopropylphenyl)imino)pent-2-en-2-yl)amino)ethyl)imino)pent-2-en-2-yl)-2,6-diisopropylaniline), was deprotonated with ZnEt2 to afford [LZn2Et2] (1). Reactions of 1 with 2 equiv of BnOH and nBuOH, respectively, gave access to [LZn2(OBn)2]·C6H14 (2·C6H14) and [LZn2(OnBu)2] (3). Treatment of 1 with 2 equiv of I2 in THF produced [LZn2I2(THF)2]·2THF (4·2THF). X-ray single-crystal diffraction analyses revealed that they are all heteroleptic bimetallic compounds with two metal centers being chelated by one ligand set. The structurally similar compounds 1 and 4·2THF possess approximate C2 symmetry, with two β-diketiminate units being arrayed in head-to-tail antiparallel mode. Thus, the molecular structures of 1 and 4·2THF exhibit a seesaw-like topology. The structures of 2·C6H14 and 3 are almost identical, in which two zinc atoms are shared by two ZnN2C3 six-membered rings, two Zn2ON2C2 seven-membered rings, and one Zn2O2 four-membered ring. Therefore, the metal cores of 2·C6H14 and 3 display a crownlike topology. All complexes are catalytically active for the borylation of aryl iodides with B2Pin2 (B2Pin2 = 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis(1,3,2-dioxaborolane). Complex 1 shows higher activity in comparison to 2, 3, and 4·2THF. The borylation reactions catalyzed by 1 could proceed under mild conditions and can be applied to a series of substrates with high functional group generality. This methodology thus represents a novel use of β-diketiminate zinc complexes for C-I borylation.
- Li, Yafei,Dang, Yan,Li, Dawei,Pan, Huifen,Zhang, Liang,Wang, Li,Cao, Zhu,Li, Yahong
-
supporting information
p. 482 - 489
(2021/03/01)
-
- Method for preparing polyfluorobenzonitrile through catalytic fluorination of polychlorobenzonitrile
-
The invention discloses a method for preparing polyfluorobenzonitrile through catalytic fluorination of polychlorobenzonitrile, and belongs to the field of preparation of fine chemical industry intermediates. The preparation method comprises the following steps: carrying out a heating activation reaction on a fluoride salt, an organic solvent and electron-withdrawing substituted phenylborate; andadding polychlorobenzonitrile, heating to 80-120 DEG C, rectifying while reacting, then supplementing polychlorobenzonitrile and potassium fluoride, and rectifying while reacting to obtain polyfluorobenzonitrile. According to the invention, the reaction system is high in catalytic activity, the technical problems of low conversion rate/medium selectivity and the like of the single nitrile compounds with low activity during fluoridation reactions are solved, the mode simultaneously performing reacting and product distilling in the reaction process promotes the continuous forward proceeding of the reaction so as to improve the reaction yield, and the method is suitable for industrial production.
- -
-
Paragraph 0023-0026
(2020/04/22)
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- Borylation of Diazonium Salts by Highly Emissive and Crystalline Carbon Dots in Water
-
Efficient borylation reaction of diazonium salts in water is realized for the first time by using easily prepared, highly emissive and crystalline carbon dots. Electron-donating and electron-withdrawing groups on diazonium salts were well tolerated with moderate to good conversion efficiency. Compared with widely used metal complexes, organic dyes and quantum dots, the approach presented herein uses carbon dots, which are nontoxic and possess good biological and medicinal compatibility and high reactivity. Therefore, this approach presents a new prospective use for carbon dots in green chemistry.
- Lei, Tao,Wei, Si-Meng,Feng, Ke,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
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p. 1715 - 1719
(2020/03/23)
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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
-
supporting information
p. 17039 - 17047
(2020/11/10)
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- Rh-Catalyzed Base-Free Decarbonylative Borylation of Twisted Amides
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We report the rhodium-catalyzed base-free decarbonylative borylation of twisted amides. The synthesis of versatile arylboronate esters from aryl twisted amides is achieved via decarbonylative rhodium(I) catalysis and highly selective N-C(O) insertion. The method is notable for a very practical, additive-free Rh(I) catalyst system. The method shows broad functional group tolerance and excellent substrate scope, including site-selective decarbonylative borylation/Heck cross-coupling via divergent N-C/C-Br cleavage and late-stage pharmaceutical borylation.
- Bie, Fusheng,Liu, Xuejing,Shi, Yijun,Cao, Han,Han, Ying,Szostak, Michal,Liu, Chengwei,Liu, Xuejing,Szostak, Michal,Liu, Chengwei
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p. 15676 - 15685
(2020/11/13)
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- Orthogonal Stability and Reactivity of Aryl Germanes Enables Rapid and Selective (Multi)Halogenations
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While halogenation is of key importance in synthesis and radioimaging, the currently available repertoire is largely designed to introduce a single halogen per molecule. This report makes the selective introduction of several different halogens accessible. Showcased here is the privileged stability of nontoxic aryl germanes under harsh fluorination conditions (that allow selective fluorination in their presence), while displaying superior reactivity and functional-group tolerance in electrophilic iodinations and brominations, outcompeting silanes or boronic esters under rapid and additive-free conditions. Mechanistic experiments and computational studies suggest a concerted electrophilic aromatic substitution as the underlying mechanism.
- Deckers, Kristina,Fricke, Christoph,Schoenebeck, Franziska
-
supporting information
p. 18717 - 18722
(2020/08/25)
-
- Direct C?H Borylation of Arenes Catalyzed by Saturated Hydride-Boryl-Iridium-POP Complexes: Kinetic Analysis of the Elemental Steps
-
The saturated trihydride IrH3{κ3-P,O,P-[xant(PiPr2)2]} (1; xant(PiPr2)2=9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) activates the B?H bond of two molecules of pinacolborane (HBpin) to give H2, the hydride-boryl derivatives IrH2(Bpin){κ3-P,O,P-[xant(PiPr2)2]} (2) and IrH(Bpin)2{κ3-P,O,P-[xant(PiPr2)2]} (3) in a sequential manner. Complex 3 activates a C?H bond of two molecules of benzene to form PhBpin and regenerates 2 and 1, also in a sequential manner. Thus, complexes 1, 2, and 3 define two cycles for the catalytic direct C?H borylation of arenes with HBpin, which have dihydride 2 as a common intermediate. C?H bond activation of the arenes is the rate-determining step of both cycles, as the C?H oxidative addition to 3 is faster than to 2. The results from a kinetic study of the reactions of 1 and 2 with HBpin support a cooperative function of the hydride ligands in the B?H bond activation. The addition of the boron atom of the borane to a hydride facilitates the coordination of the B?H bond through the formation of κ1- and κ2-dihydrideborate intermediates.
- Esteruelas, Miguel A.,Martínez, Antonio,Oliván, Montserrat,O?ate, Enrique
-
supporting information
p. 12632 - 12644
(2020/09/09)
-
- Luminescent tungsten(vi) complexes as photocatalysts for light-driven C-C and C-B bond formation reactions
-
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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- Reductive Electrophotocatalysis: Merging Electricity and Light to Achieve Extreme Reduction Potentials
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We describe a new electrophotocatalytic strategy that harnesses the power of light and electricity to generate an excited radical anion with a reducing potential of -3.2 V vs SCE, which can be used to activate substrates with very high reduction potentials (Ered ≈ -1.9 to -2.9 V). The resultant aryl radicals can be engaged in various synthetically useful transformations to furnish arylboronate, arylstannane, and biaryl products.
- Kim, Hyunwoo,Kim, Hyungjun,Lambert, Tristan H.,Lin, Song
-
supporting information
p. 2087 - 2092
(2020/02/04)
-
- Para-selective borylation of monosubstituted benzenes using a transient mediator
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Herein, we conceptualized a transient mediator approach that has the capability of para-selective C-H functionalization of monosubstituted aromatics. This approach is enabled by in situ generation of a versatile sulfonium salt via highly electrophilic phenoxathiine or thianthrene dication intermediate which can be readily generated from its sulfoxide with trifluoromethanesulfonic anhydride. Preliminary mechanistic study implied that the remarkable para selectivity might be related to the incredible electrophilicity of thianthrene dication intermediate. The versatility of this approach was demonstrated via para-borylation of various monosubstituted simple aromatics combining the sulfonium salt formation with further photocatalyzed transformation.
- Wu, Jie,Wang, Zengwei,Chen, Xiao-Yue,Wu, Yichen,Wang, Daoming,Peng, Qian,Wang, Peng
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p. 336 - 340
(2019/12/09)
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- Chemoselective Rhodium-Catalyzed Borylation of Bromoiodoarenes under Mild Conditions
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A chemoselective rhodium-catalyzed borylation has been developed for the preparation of aryl boronate esters. The reaction proceeds under mild conditions with excellent selectivity for C-I bonds in bromoiodoarenes and exhibits broad functional group tolerance. This procedure can act as a complementary approach toward bifunctional arenes along with other metal-catalyzed borylations. Additionally, the reaction's utility in the preparation of monomers for metal-catalyzed cross-coupling polymerization is demonstrated.
- Varni, Anthony J.,Bautista, Michael V.,Noonan, Kevin J.T.
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p. 6770 - 6777
(2020/07/21)
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- Mild, Selective Ru-Catalyzed Deuteration Using D2O as a Deuterium Source
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A method for the selective deuteration of polyfunctional organic molecules using catalytic amounts of [RuCl2(PPh3)3] and D2O as a deuterium source is presented. Through variation of additives like CuI, KOH, and various amounts of zinc powder, orthogonal chemoselectivities in the deuteration process are observed. Mechanistic investigation indicates the presence of different, defined Ru-complexes under the given specific conditions.
- Eisele, Pascal,Ullwer, Franziska,Scholz, Sven,Plietker, Bernd
-
supporting information
p. 16550 - 16554
(2019/12/11)
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- Vinylidenation of Organoboronic Esters Enabled by a Pd-Catalyzed Metallate Shift
-
Organoboron “ate” complexes undergo a net vinyl insertion reaction to give 1,1-disubstituted alkenyl boronic esters when treated with stoichiometric allyl acetate and a palladium catalyst. Reactions that employ vinyllithium afforded good to excellent yields after one hour, while reactions that employ vinylmagnesium chloride furnished modest to good yields after 18 hours.
- Aparece, Mark D.,Gao, Chenpeng,Lovinger, Gabriel J.,Morken, James P.
-
supporting information
p. 592 - 595
(2019/01/04)
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- Photocatalyzed borylation using water-soluble quantum dots
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The synthesis of arylboronates by Sandmeyer-type reactions in the presence of water still remains a significant challenge. Herein, we report the use of water-soluble MPA-capped quantum dot (QD) photocatalysts for the borylation of diazonium salts in the presence of water. A biphasic system under mild acidic conditions remains critical to prevent decomposition and competitive disulphide bond formation. The present protocol offers a broader scope of substrates and borylating agents. Additionally, this catalytic system offers a significantly high turnover number (TON). The present methodology can effectively distinguish subtle reactivity differences between boronic acids and boronates. Mechanistic investigation suggests an excited-state electron transfer pathway.
- Chandrashekar, Hediyala B.,Maji, Arun,Halder, Ganga,Banerjee, Sucheta,Bhattacharyya, Sayan,Maiti, Debabrata
-
supporting information
p. 6201 - 6204
(2019/06/07)
-
- Redox reactions of small organic molecules using ball milling and piezoelectric materials
-
Over the past decade, photoredox catalysis has harnessed light energy to accelerate bond-forming reactions. We postulated that a complementary method for the redox-activation of small organic molecules in response to applied mechanical energy could be dev
- Kubota, Koji,Pang, Yadong,Miura, Akira,Ito, Hajime
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p. 1500 - 1504
(2020/01/08)
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- Redox-Neutral Borylation of Aryl Sulfonium Salts via C-S Activation Enabled by Light
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Reported here is a novel photoinduced strategy for the borylation of aryl sulfonium salts using bis(pinacolato)diboron as the boron source. This method exploits redox-neutral aryl sulfoniums to gain access to aryl radicals via C-S bond activation upon photoexcitation under transition-metal-free conditions. Therefore, it grants access to diverse arylboronate esters with good performance from easily available aryl sulfoniums accompanied by mild conditions, operational simplicity, and easy scalability.
- Huang, Chen,Feng, Jie,Ma, Rui,Fang, Shuaishuai,Lu, Tao,Tang, Weifang,Du, Ding,Gao, Jian
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p. 9688 - 9692
(2019/12/02)
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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
-
supporting information
p. 5392 - 5395
(2019/03/29)
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- Visible light-promoted formation of C-B and C-S bonds under metal- A nd photocatalyst-free conditions
-
A green, efficient, photoinduced synthesis of arylboronic esters and aryl sulfides has been developed. Bench stable arylazo sulfones were used as radical precursors for a photocatalyst- A nd additive-free carbon-heteroatom bond formation under visible light. The protocols are applicable to a wide range of substrates, providing products in good yields.
- Blank, Lena,Fagnoni, Maurizio,Protti, Stefano,Rueping, Magnus
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p. 1243 - 1252
(2019/02/26)
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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
-
supporting information
p. 3262 - 3266
(2019/02/13)
-
- Additive- and Photocatalyst-Free Borylation of Arylazo Sulfones under Visible Light
-
We developed a photocatalyst-free and additive-free, visible light induced borylation reaction using arylazo sulfones as starting material. This protocol shows some advantages such as mild conditions, simple equipment, and wide substrate scope, which gives a complementary protocol for the preparation of arylboronates.
- Xu, Yuliang,Yang, Xinying,Fang, Hao
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p. 12831 - 12837
(2018/10/20)
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- METHODS OF MANUFACTURING OF BORON COMPOUND WITHOUT TRANSITION METALS
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The present invention refers to aryl boron compound number bath method relates to search, more particularly transition metal catalyst to a tank without the use of boron compounds number is given to the aryl organic halo [ceyn [ceyn] freight method are disclosed to boron. (by machine translation)
- -
-
Paragraph 0062; 0063; 0071; 0072; 0076
(2018/05/03)
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- Alcohol-initiated dediazoniation of aryldiazonium ions to aryl radicals: A simple and efficient route to arylboronates
-
A simple and efficient access to arylboronates was achieved with methanol-initiated borylation of aryldiazonium salts. Reduction of aryldiazonium ions by single electron transfer from methanol affords aryl radical species, which undergo a subsequent C?B bond formation with bis(pinacolato)diboron. This highly practical borylation process, which can be carried out on the gram-scale, enjoys operational simplicity as well as mild and catalyst-free conditions.
- Zhang, Xiulian,Zhang, Zhicheng,Xie, Yongbin,Jiang, Yujie,Xu, Ruibo,Luo, Yuhui,Tao, Chuanzhou
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p. 481 - 485
(2018/10/15)
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- Palladium(I) Dimer Enabled Extremely Rapid and Chemoselective Alkylation of Aryl Bromides over Triflates and Chlorides in Air
-
Disclosed herein is the first general chemo- and site-selective alkylation of C?Br bonds in the presence of COTf, C?Cl and other potentially reactive functional groups, using the air-, moisture-, and thermally stable dinuclear PdI catalyst, [Pd(μ-I)PtBu3]2. The bromo-selectivity is independent of the substrate and the relative positioning of the competing reaction sites, and as such fully predictable. Primary and secondary alkyl chains were introduced with extremely high speed (5 min reaction time) at room temperature and under open-flask reaction conditions.
- Kalvet, Indrek,Sperger, Theresa,Scattolin, Thomas,Magnin, Guillaume,Schoenebeck, Franziska
-
supporting information
p. 7078 - 7082
(2017/06/13)
-
- Pd-Catalyzed Conjunctive Cross-Coupling between Grignard-Derived Boron “Ate” Complexes and C(sp2) Halides or Triflates: NaOTf as a Grignard Activator and Halide Scavenger
-
Catalytic enantioselective conjunctive cross-couplings that employ Grignard reagents are shown to furnish an array of nonracemic chiral organoboronic esters in an efficient and highly selective fashion. The utility of sodium triflate in facilitating this reaction is two-fold: it enables “ate” complex formation and overcomes catalytic inhibition by halide ions.
- Lovinger, Gabriel J.,Aparece, Mark D.,Morken, James P.
-
supporting information
p. 3153 - 3160
(2017/03/11)
-
- Ni-Catalyzed Enantioselective Conjunctive Coupling with C(sp3) Electrophiles: A Radical-Ionic Mechanistic Dichotomy
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The catalytic enantioselective conjunctive coupling of C(sp3) electrophiles can be accomplished with Ni catalysis. The enantioselectivity of the reaction is dependent on reaction mechanism with many substrates able to engage in an asymmetric process with Pybox-Ni complexes, whereas other substrates provide racemic product mixtures. The link between substrate structure and selectivity is addressed.
- Lovinger, Gabriel J.,Morken, James P.
-
supporting information
p. 17293 - 17296
(2017/12/15)
-
- Convenient and General Zinc-Catalyzed Borylation of Aryl Diazonium Salts and Aryltriazenes under Mild Conditions
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A convenient and general zinc-catalyzed borylation of aryl diazonium salts and aryltriazenes has been developed. With bis- (pinacolato)diboron as the borylation reagent, aryldiazonium tetrafluoroborate salts and aryltriazenes were transformed into the corresponding arylboronates in moderate to excellent yields under mild conditions. As a convenient and practical methodology, no additional ligands, base, or any other additives are required here.
- Qi, Xinxin,Jiang, Li-Bing,Zhou, Chao,Peng, Jin-Bao,Wu, Xiao-Feng
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p. 345 - 349
(2017/06/23)
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- Mechanochemical borylation of aryldiazonium salts; merging light and ball milling
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Merging of photo- and mechanochemical activation permitted studying the role of eosin Y in the borylation of aryldiazonium salts in a ball mill. Simultaneous neat grinding/irradiation of the reactants and the photocatalyst led to the formation of boronates in a molten state. On the other hand, the catalyst-free liquid-assisted grinding/irradiation reaction also led to product formation, featuring a direct photolysis pathway facilitated by substrate–solvent charge-transfer complex formation.
- Hernández, José G.
-
supporting information
p. 1463 - 1469
(2017/08/02)
-
- Transition-Metal-Free, Visible-Light-Enabled Decarboxylative Borylation of Aryl N-Hydroxyphthalimide Esters
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Herein, we report a conceptually novel borylation reaction proceeding via a mild photoinduced decarboxylation of redox-activated aromatic carboxylic acids. This work constitutes the first application of cheap and easily prepared N-hydroxyphthalimide esters as aryl radical precursors and does not require the use of expensive transition metals or ligands. The reaction is operationally simple, scalable, and displays broad scope and functional group tolerance.
- Candish, Lisa,Teders, Michael,Glorius, Frank
-
supporting information
p. 7440 - 7443
(2017/06/13)
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- Chemoselective coupling of 1,1-bis[(pinacolato)boryl]alkanes for the transition-metal-frec borylation of aryl and vinyl halides: A combined experimental and theoretical investigation
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A new transition-metal-frec borylation of aryl and vinyl halides using l,l-bis[(pinacolato)boryl]alkanes as boron sources is described. In this transformation one of the boron groups from 1,1-bis[(pinacolato)boryl]alkanes is selectively transferred to aryl and vinyl halides in the presence of sodium tert-butoxide as the only activator to form organoboronate esters. Under the developed borylation conditions, a broad range of organohalides are borylated with excellent chemo-selectivity and functional group compatibility, thus offering a rare example of a transition-metal-frec borylation protocol. Experimental and theoretical studies have becn performed to elucidate the reaction mechanism, revealing the unusual formation of Lewis acid/base adduct betwecn organohalides and α-borylcarbanion, generated in situ from the reaction of l,l-bis[(pinacolato)boryl]alkanes with an alkoxide base, to facilitate the borylation reactions.
- Lee, Yeosan,Baek, Seung-Yeol,Park, Jinyoung,Kim, Seoung-Tae,Tussupbayev, Samat,Kim, Jeongho,Baik, Mu-Hyun,Cho, Seung Hwan
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p. 975 - 984
(2017/05/16)
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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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- 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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- Borylation of aryldiazonium salts at room temperature in an aqueous solution under catalyst-free conditions
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A general and convenient borylation reaction of aryldiazonium tetrafluoroborate salts with B2pin2 has been developed. In this catalytic system, no catalyst, additional ligands or additives were required. The reaction proceeded smoothly in an aqueous solution, and a variety of arylboronates were isolated in moderate to excellent yields under mild reaction conditions.
- Qi, Xinxin,Li, Hao-Peng,Peng, Jin-Bao,Wu, Xiao-Feng
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supporting information
p. 3851 - 3853
(2017/09/15)
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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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- 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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- One-pot Suzuki coupling of aromatic amines via visible light photocatalyzed metal free borylation using t-BuONO at room temperature
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A convenient and efficient metal free borylation of aromatic amines has been achieved using tertiary butyl nitrite and B2Pin2 (bis(pinacolato)diborane) under irradiation with blue LED light at room temperature. This protocol has been successfully extended to subsequent Suzuki coupling in the same pot. Thus a series of functionalized aryl boronates and biaryls are obtained in high yields in a shorter reaction period starting from relatively cheap aryl amines in one-pot avoiding isolation of potentially unstable and hazardous intermediates.
- Ahammed, Sabir,Nandi, Shiny,Kundu, Debasish,Ranu, Brindaban C.
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p. 1551 - 1554
(2018/03/29)
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- Emitting polymer and organic emitting device the emitting polymer
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Provided are compounds containing a phosphorescence unit, an emitting polymer, and an organic light emitting device (OLED) containing an organic layer including the emitting polymer. The OLED is useful in portable electronic equipment where low power consumption and low driving voltage are desirable.
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Paragraph 0217-0222
(2017/01/17)
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- Regioselective electrophilic borylation of haloarenes
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Haloarenes undergo direct borylation using amine:BCl3:AlCl3 in the ratio of 1:1:2. After esterification the pinacol boronate esters are isolated in good yield with regioselectivity controlled by steric and electronic effects.
- Del Grosso, Alessandro,Ayuso Carrillo, Josue,Ingleson, Michael J.
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supporting information
p. 2878 - 2881
(2015/02/19)
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- A mild carbon-boron bond formation from diaryliodonium salts
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The direct metal-free borylation of diaryliodonium salts with diboron reagents is now demonstrated to be a feasible process toward formation of aryl boronic esters without any additive or catalysts, and it can be extended to a two-step C-C coupling of both aryl groups of the initial diaryliodonium reagent.
- Miralles,Romero,Fernández,Mu?iz
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p. 14068 - 14071
(2015/09/15)
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- Synthesis, structure, and reactivity of anionic sp2-sp3 diboron compounds: Readily accessible boryl nucleophiles
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Lewis base adducts of tetra-alkoxy diboron compounds, in particular bis(pinacolato)diboron (B2pin2), have been proposed as the active source of nucleophilic boryl species in metal-free borylation reactions. We report the isolation and detailed structural characterization (by solid-state and solution NMR spectroscopy and X-ray crystallography) of a series of anionic adducts of B2pin2 with hard Lewis bases, such as alkoxides and fluoride. The study was extended to alternative Lewis bases, such as acetate, and other diboron reagents. The B(sp2)-B(sp3) adducts exhibit two distinct boron environments in the solid-state and solution NMR spectra, except for [(4-tBuC6H4O)B2pin2]-, which shows rapid site exchange in solution. DFT calculations were performed to analyze the stability of the adducts with respect to dissociation. Stoichiometric reaction of the isolated adducts with two representative series of organic electrophiles - namely, aryl halides and diazonium salts - demonstrate the relative reactivities of the anionic diboron compounds as nucleophilic boryl anion sources.
- Pietsch, Sabrina,Neeve, Emily C.,Apperley, David C.,Bertermann, Rüdiger,Mo, Fanyang,Qiu, Di,Cheung, Man Sing,Dang, Li,Wang, Jianbo,Radius, Udo,Lin, Zhenyang,Kleeberg, Christian,Marder, Todd B.
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supporting information
p. 7082 - 7099
(2015/05/05)
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- A Bicyclic N-Heterocyclic Carbene as a Bulky but Accessible Ligand: Application to the Copper-Catalyzed Borylations of Aryl Halides
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Imidazol-2-ylidene and imidazolin-2-ylidene are frequently employed as the core structures of N-heterocyclic carbene (NHC) ligands, because these have two nitrogen sites adjacent to carbenic carbons. The electronic and steric effects of N-substituents to a bound metal have been aptly studied, and bulky substituents have commonly been introduced on nitrogen(s). However, too much bulkiness can sometimes result in an ineffectiveness of the hindered substrates. In this study, we thoroughly compared our original bicyclic NHC, which has bulky substituents on its noncarbenic carbons, with ubiquitous NHC ligands to probe its steric properties. A well-defined bicyclic NHC-CuCl complex was successfully synthesized and applied to the copper-catalyzed borylations of aryl halides at ambient temperature. A bicyclic NHC-CuCl proved to be a better catalyst than commonly used NHC ligand-Cu complexes, particularly for sterically hindered substrates, which suggested that the bicyclic NHC ligand offered a bulky but accessible environment to the bound copper.
- Ando, Shin,Matsunaga, Hirofumi,Ishizuka, Tadao
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p. 9671 - 9681
(2015/10/12)
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- On the mechanism of photocatalytic reactions with eosin y
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A combined spectroscopic, synthetic, and apparative study has allowed a more detailed mechanistic rationalization of several recently reported eosin Y-catalyzed aromatic substitutions at arenediazonium salts. The operation of rapid acid-base equilibria, direct photolysis pathways, and radical chain reactions has been discussed on the basis of pH, solvent polarity, lamp type, absorption properties, and quantum yields. Determination of the latter proved to be an especially valuable tool for the distinction between radical chain and photocatalytic reactions. 2014 Majek et al; licensee Beilstein-Institut.
- Majek, Majek,Filace, Fabiana,Von Wangelin, Axel Jacobi
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p. 981 - 989
(2014/05/20)
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- Application of cooperative iron/copper catalysis to a palladium-free borylation of aryl bromides with pinacolborane
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A new cooperative copper/iron catalysis for the borylation of various aryl bromides with pinacolborane, at -10 °C, is reported. Use of the toxic, precious metal Pd is avoided. The mechanism of the protodebromination side reaction is discussed.
- Labre, Flavien,Gimbert, Yves,Bannwarth, Pierre,Olivero, Sandra,Dunach, Elisabet,Chavant, Pierre Y.
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supporting information
p. 2366 - 2369
(2014/05/20)
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- Borylation using group IV metallocene under mild conditions
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A borylation reaction of aromatic diazonium salts has been optimized using titanocene and zirconocene derivatives as catalysts. The reaction employs diisopropylaminoborane as a borylating agent and proceeds smoothly at room temperature to provide arylboronates after methanolysis and transesterification with pinacol. The reaction mechanism has been found to proceed via a radical pathway.
- Marciasini, Ludovic D.,Vaultier, Michel,Pucheault, Mathieu
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p. 1702 - 1705
(2014/03/21)
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- NEW PROCESS FOR PREPARING ARYLBORANES BY ARYLATION OF ORGANOBORON COMPOUNDS
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The present invention relates to a new process for the preparation of an arylborane compound, by arylation of a B-H bond, which comprises a step (1) of contacting an arenediazonium salt or a heteroarenediazonium salt with an organoboron compound containing at least one B-H bond, in a reaction medium containing a solvent, in the absence of base, in the absence or in the presence of an activating agent, for the preparation of an arylborane compound, and a possible step (2) of recovery and purification of said arylborane compound obtained at the step (1), said arylborane being in particular an aminoarylborane, and a possible step (3) of refunctionalisation of said arylborane obtained at step (1) or (2) for the preparation of aryl boronic derivatives or arylborates.
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Page/Page column 64
(2014/02/15)
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