- Light- and Manganese-Initiated Borylation of Aryl Diazonium Salts: Mechanistic Insight on the Ultrafast Time-Scale Revealed by Time-Resolved Spectroscopic Analysis
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Manganese-mediated borylation of aryl/heteroaryl diazonium salts emerges as a general and versatile synthetic methodology for the synthesis of the corresponding boronate esters. The reaction proved an ideal testing ground for delineating the Mn species responsible for the photochemical reaction processes, that is, involving either Mn radical or Mn cationic species, which is dependent on the presence of a suitably strong oxidant. Our findings are important for a plethora of processes employing Mn-containing carbonyl species as initiators and/or catalysts, which have considerable potential in synthetic applications.
- Firth, James D.,Hammarback, L. Anders,Burden, Thomas J.,Eastwood, Jonathan B.,Donald, James R.,Horbaczewskyj, Chris S.,McRobie, Matthew T.,Tramaseur, Adam,Clark, Ian P.,Towrie, Michael,Robinson, Alan,Krieger, Jean-Philippe,Lynam, Jason M.,Fairlamb, Ian J. S.
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supporting information
p. 3979 - 3985
(2021/02/03)
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- Synthesis of arylboronates via the Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates with bis(pinacolato)diboron
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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
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- Borylation of Diazonium Salts by Highly Emissive and Crystalline Carbon Dots in Water
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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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- Direct C?H Borylation of Arenes Catalyzed by Saturated Hydride-Boryl-Iridium-POP Complexes: Kinetic Analysis of the Elemental Steps
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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
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supporting information
p. 12632 - 12644
(2020/09/09)
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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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- 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
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supporting information
p. 6201 - 6204
(2019/06/07)
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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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- Alcohol-initiated dediazoniation of aryldiazonium ions to aryl radicals: A simple and efficient route to arylboronates
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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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- 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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- 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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p. 4291 - 4294
(2017/08/23)
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- Green light iridium (III) complex and a method of preparing the same
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The present invention provides a green light iridium (III) complex and a method of preparing the same, which has a formula as follows: wherein m is 2 or 3; at least one of Ar1, Ar2, Ar3, Ar4, and Ar5
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Page/Page column 9
(2016/05/09)
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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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- EZH2 INHIBITORS AND USES THEREOF
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The present invention provides compound of formula 1, or an isotopic form, a stereoisomer, a tautomer, a pharmaceutically acceptable salt, a solvate, a polymorph, a prodrug, S-oxide or N-oxide thereof. The invention also relates toprocesses for their preparation, to pharmaceutical compositions containing them and use of the compound of formula 1, in the treatment of diseases or disorders mediated by EZH2 (enhancer of zeste homolog 2), particularly cancer.
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Page/Page column 63
(2015/08/06)
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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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Paragraph 0108; 0109; 0110; 0111; 0156; 0157
(2014/01/23)
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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 63-64
(2014/02/15)
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- Iron-catalysed borylation of arenediazonium salts to give access to arylboron derivatives via aryl(amino)boranes at room temperature
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Complementary to previously described Miyaura borylation methods, a new access to boron derivatives via aryl(amino)boranes is described. Direct coupling between aryldiazonium salts and diisopropylaminoborane is catalysed by 0.1% ferrocene leading to the formation of a carbon-boron bond. The obtained aryl(amino)boranes could eventually then be transformed into boronic acids, boronates or borates. Copyright
- Marciasini, Ludovic D.,Richy, Nicolas,Vaultier, Michel,Pucheault, Mathieu
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supporting information
p. 1083 - 1088
(2013/05/21)
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- Synthesis of pinacol arylboronates from aromatic amines: A metal-free transformation
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A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.
- Qiu, Di,Jin, Liang,Zheng, Zhitong,Meng, He,Mo, Fanyang,Wang, Xi,Zhang, Yan,Wang, Jianbo
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p. 1923 - 1933
(2013/03/29)
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- Transition-metal-free borylation of aryltriazene mediated by BF 3·OEt2
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A practical and simple method for deaminoborylation of aryltriazene with bis(pinacolato)diboron has been developed that is mediated by BF 3·OEt2. Various arylboronic esters are prepared in moderate to good yields with this facile transition-metal-free procedure.
- Zhu, Chuan,Yamane, Motoki
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p. 4560 - 4563
(2012/10/30)
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- Gold(iii)-catalyzed halogenation of aromatic boronates with N -halosuccinimides
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Aromatic boronates bearing halogen substituents in the aromatic ring can be synthesized by AuCl3-catalyzed halogenations with N-halosuccinimides.
- Qiu, Di,Mo, Fanyang,Zheng, Zhitong,Zhang, Yan,Wang, Jianbo
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scheme or table
p. 5474 - 5477
(2011/02/22)
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- Use of in situ isopropoxide protection in the metal-halogen exchange of arylboronates
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(Chemical Equation Presented) Isopropoxide protection of arylboronates allowed their use in metal-halogen exchange reactions. The isopropoxide- protected borate species were obtained from a boronate or in situ from dibromoarenes. meta- and para-dibromoare
- Jiang, Qin,Ryan, Meagan,Zhichkin, Paul
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p. 6618 - 6620
(2008/02/10)
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- Electrochemical reduction of polyhalogenated aryl derivatives in the presence of pinacolborane: Electrosynthesis of functionalised arylboronic esters
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The electroreduction of several dihalogenated aryl compounds was carried out in the presence of pinacolborane as the electrophile for the synthesis of halogenated arylboronic ester derivatives. The nature and the relative position of the halogen substituents strongly influence the boration results. The electroreduction of a trihalogenated derivative was also examined. Reactions were carried out in THF in a single-compartment cell in the presence of a Mg anode.
- Laza,Pintaric,Olivero,Dunach
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p. 4897 - 4901
(2008/10/09)
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- PHARMACEUTICAL USE OF BORONIC ACIDS AND ESTERS THEREOF
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Use of compounds to inhibit hormone-sensitive lipase, the use of these compounds as pharmaceutical compositions, pharmaceutical compositions comprising the compounds, method of treatment employing these compounds and compositions, and novel compounds. The present compounds are inhibitors of hormone-sensitve lipase and may be useful in the treatment and/or prevention of a range of medical disorders where a decreased activity of hormone-sensitive lipase is desirable.
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