- Multiple fluorescent behaviors of phenothiazine-based organic molecules
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We have designed a conventional one-step Suzuki coupling synthetic method to prepare 3,7-di-aryl substituted 10H-phenothiazine derivatives and investigated their optical behaviors. The compound 3,7-Bis (4-aminophenyl) phenothiazine (compound 1), substituting with electron-donating aniline, can exhibit photodamage behavior toward cancer cells. Furthermore, the compound 1 can form fluorescent organic nanoparticle (FON) in acidic aqueous whereas can emit red fluorescence in alkaline organic solvent. More importantly, compound 1 can be oxidized to manufactured a stable near-IR dye (>950 nm). Alternatively, the control compound 3,7-Bis (4-nitrophenyl) phenothiazine (compound 2) enabled us to determine that an electron-withdrawing group, when attaching on the phenothiazine, is unfavorable for molecular design to manufacture a cation form of NIR dye but is favorable to stabilize the phenothiazinate core and manufacture an anion form of NIR dye.
- Hsieh, Tung-Sheng,Wu, Jhen-Yi,Chang, Cheng-Chung
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Read Online
- 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.
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Read Online
- Improvement in the Palladium-Catalyzed Miyaura Borylation Reaction by Optimization of the Base: Scope and Mechanistic Study
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Aryl boronic acids and esters are important building blocks in API synthesis. The palladium-catalyzed Suzuki-Miyaura borylation is the most common method for their preparation. This paper describes an improvement of the current reaction conditions. By using lipophilic bases such as potassium 2-ethyl hexanoate, the borylation reaction could be achieved at 35 °C in less than 2 h with very low palladium loading (0.5 mol %). A preliminary mechanistic study shows a hitherto unrecognized inhibitory effect by the carboxylate anion on the catalytic cycle, whereas 2-ethyl hexanoate minimizes this inhibitory effect. This improved methodology enables borylation of a wide range of substrates under mild conditions.
- Barroso, Santiago,Joksch, Markus,Puylaert, Pim,Tin, Sergey,Bell, Stephen J.,Donnellan, Luke,Duguid, Stewart,Muir, Colin,Zhao, Peichao,Farina, Vittorio,Tran, Duc N.,De Vries, Johannes G.
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supporting information
p. 103 - 109
(2020/12/22)
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- Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
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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
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supporting information
p. 15396 - 15405
(2021/10/12)
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- Impact of Five-membered Heterocyclic Rings on Photophysical Properties including Two-photon Absorption Character
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A series of dipolar-type terphenyl derivatives 13 featuring an electron donor (p-NMe2C6H4 group) and acceptor (p-NO2C6H4 group) unit was synthesized and their photophysical properties were
- Abe, Manabu,Chitose, Youhei,Lin, Tzu-Chau,Pham, Thuy Thi Thu,Tam, Tran Thi Thanh,Tseng, Wei-Lun
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supporting information
p. 1810 - 1813
(2021/10/27)
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- COMPOUNDS FOR TARGETED DEGRADATION OF BRD9
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BRD9 protein degradation compounds or pharmaceutically acceptable salts thereof are provided for the treatment of disorders mediated by BRD9, including but not limited to abnormal cellular proliferation.
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Page/Page column 512-513
(2021/09/11)
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- 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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- 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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- 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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- Photocatalytic C–X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles
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Hierarchical SiC nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C-X (X = Br, I) borylation of aryl halides at 30 °C. The SiC/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from SiC to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C-I or C-Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/SiC photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.
- Jiao, Zhi-Feng,Zhao, Ji-Xiao,Guo, Xiao-Ning,Guo, Xiang-Yun
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p. 357 - 363
(2019/12/28)
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- Facile and economical Miyaura borylation and one-pot Suzuki–Miyaura cross-coupling reaction
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Facile and economical method for Miyaura borylation reaction between B2pin2 and aryl bromides is reported. The catalytic system containing 2 mol% PdCl2(PPh3)2 and KOAc serves to enable borylations to occur under solvent-free and atmospheric conditions. The developed protocol can be applied to synthesize symmetrical and unsymmetrical biaryls via one-pot two-step Suzuki–Miyaura cross-coupling reaction and also offers the up-scalability.
- Boontiem, Phongsakorn,Kiatisevi, Supavadee
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supporting information
(2020/03/03)
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- Fluorene derivative fluorescent material, preparation method thereof, and application of fluorene derivative fluorescent material in detecting gas-phase phthalate plasticizers
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The invention provides a fluorene derivative fluorescent material as shown in a formula (I), a preparation method thereof, and an application of the fluorene derivative fluorescent material in detecting gas-phase phthalate plasticizers, wherein the fluore
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Paragraph 0087-0091; 0106-0109
(2020/02/14)
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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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- Visible light-promoted formation of C-B and C-S bonds under metal- A nd photocatalyst-free conditions
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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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- Pd(II) Complexes with Chelating Phosphinoferrocene Diaminocarbene Ligands: Synthesis, Characterization, and Catalytic Use in Pd-Catalyzed Borylation of Aryl Bromides
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We developed a novel, straightforward route toward Pd(II)-aminocarbene complexes bearing a P-chelating phosphinoferrocenyl substituent based on a three-component reaction of 1′-(diphenylphosphino)-1-isocyanoferrocene (1) with [PdCl2(cod)] (cod = cycloocta-1,5-diene) and nucleophilic amines. Depending on the type of the amine, the reaction produced acyclic diaminocarbenes and their saturated (imidazolin-2-ylidene) and unsaturated (imidazol-2-ylidene) cyclic counterparts (NHCs). Using (S)-2-(chloromethyl)pyrrolidine as the nucleophile, this method afforded a separable pair of stable diastereomeric bicyclic imidazolin-2-ylidene carbenes with different configurations of the planar-chiral ferrocene unit. The prepared P-chelating carbenes were characterized using spectroscopic methods, X-ray crystallography, and DFT methods. The last were used to explain the formation of isomeric open diaminocarbenes featuring NHR groups at the wing-tip position, trends in Pd-Cl bond lengths reflecting similar trans influences of the particular carbene and phosphine donors, and the results from cyclic voltammetric measurements. Furthermore, the carbenes were used as defined (pre)catalysts in Miyaura borylation of aryl bromides with bis(pinacolato)diboron. When applying the optimized catalytic system (1 mol % Pd catalyst, KOAc as the base, 2-propanol, 85 °C), this reaction produced a range of simple and substituted arylboronate pinacol esters in high yield and without biaryl side products.
- ?koch, Karel,Schulz, Ji?í,Císa?ová, Ivana,?těpni?ka, Petr
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p. 3060 - 3073
(2019/08/20)
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- SUBSTITUTED PHENYL SULFONYL PHENYL TRIAZOLE THIONES AND USES THEREOF
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The present disclosure relates to substituted phenyl sulfonyl phenyl triazole thiones, pharmaceutical compositions containing them, and methods of using them.
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Paragraph 0180-0181
(2019/05/22)
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- METHOD OF TREATING A CONDITION ASSOCIATED WITH NEURODEGENERATION USING INHIBITORS OF OAT3
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The present disclosure relates to therapeutic agents that may be useful in treatment and prophylaxis of neurodegenerative disorders and/or neural inflammation.
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Paragraph 0278; 0280-0281
(2020/01/11)
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- Short Wavelength Inner Filter Technique (SWIFT) in Designing Reactive Fluorescent Molecular Probes
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Here, we present a conceptually novel and experimentally straightforward technique for selective analyte detection that uses a combination of commercial fluorophores and simple chemicals. The technique utilizes the well-known inner filter effect (IFE); however, the fluorophore's excitation is performed at wavelengths significantly shorter than its absorption maximum. In the presence of the analyte, the "filter" appears or disappears at the excitation wavelength resulting in the fluorescence turning OFF or ON, respectively. Unlike common probes, our technique allows real-time monitoring of a fluorophore's stability as well as its recycling. We further demonstrate the applicability of this technique in continuing analyte detection as well as vapor analysis.
- Baheti, Abhishek,Vigalok, Arkadi
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supporting information
p. 12224 - 12228
(2019/08/21)
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- Redox reactions of small organic molecules using ball milling and piezoelectric materials
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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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- Additive- and Photocatalyst-Free Borylation of Arylazo Sulfones under Visible Light
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We developed a photocatalyst-free and additive-free, visible light induced borylation reaction using arylazo sulfones as starting material. This protocol shows some advantages such as mild conditions, simple equipment, and wide substrate scope, which gives a complementary protocol for the preparation of arylboronates.
- Xu, Yuliang,Yang, Xinying,Fang, Hao
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p. 12831 - 12837
(2018/10/20)
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- 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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- Pd II -Porphyrin Complexes - The First Use as Safer and Efficient Catalysts for Miyaura Borylation
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We have developed a simple and convenient procedure for the preparation of pinacol arylboronates from aryl/heteroaryl bromides and bis(pinacolato)diborane using a Pd II -porphyrin complex as a catalyst. Seven different Pd II -porphyrin complexes (Pd II -T m HPP, Pd II -T m CPP, Pd II -TPP, Pd II -TST p SPP, Pd II -T p CPP, Pd II -T p TP, and Pd II -T p AP) have been synthesized and investigated for their catalytic influence in the Miyaura borylation.
- Rao, Kanusu Umamaheswara,Venkateswarlu, Katta
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supporting information
p. 1055 - 1060
(2018/03/23)
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- CONDENSED RING DERIVATIVE, AND PREPARATION METHOD, INTERMEDIATE, PHARMACEUTICAL COMPOSITION AND USE THEREOF
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Disclosed are a condensed ring derivative, and a preparation method, an intermediate, a pharmaceutical composition and a use thereof. The condensed ring derivative of the present invention has a significant inhibitive effect on URAT1, which can effectively alleviate or treat hyperuricemia and other related diseases.
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Paragraph 0161
(2018/02/28)
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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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- Aromatic azoxybenzene compound and preparation method thereof
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The invention discloses an aromatic azoxybenzene compound and a preparation method thereof. The preparation method comprises the following steps: firstly reducing aromatic nitro-compounds into azoxybenzene through photoinduction in an alkaline condition; firstly synthesizing different aromatic nitro-compounds; secondly, carrying out nitro reduction under the irradiation of a xenon lamp under the conditions of potassium hydroxide, methylbenzene and isopropyl alcohol, and thus synthesizing the aromatic azoxybenzene compound. The preparation method disclosed by the invention has the advantages of simple components, mild reaction conditions, low toxicity, environmental protection, high selectivity and the like; the obtained aromatic azoxybenzene compound has potential application in the aspects of dyes, liquid crystal materials, optical materials and the like.
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Paragraph 0022; 0027
(2017/10/25)
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- 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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- 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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- A method for synthesizing aromatic boric acid ester compound (by machine translation)
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The invention discloses a method for synthesizing aromatic boric acid ester compound, which belongs to the technical field of organic synthesis intermediates, the method of the present invention specifically comprises the following steps: adding acetonitrile to the reaction tube (1), aryl sulfonyl chloride, and frequency that alcohol esterjoint boric acid two potassium hydrogen, the plug of the reaction tube, the reaction tube by the ultraviolet lamp irradiated with magnetic stirring at room temperature the reaction 24 hours ; (2) after the end of the reaction, pressure reducing evaporate most of the solvent, in a volume ratio of 10:1-30:1 for showering liquid petroleum ether and ethyl acetate of the remaining mixture liquid to column chromatography separation and purification, the product is obtained. In the organic synthesis of this invention, material, medical, agricultural chemicals, and the like has wide application in the field. The invention has the advantages of low cost, simple operation, high yield, it has very good application prospects. (by machine translation)
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Paragraph 0029-0031
(2017/04/04)
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- Miyaura Borylation and One-Pot Two-Step Homocoupling of Aryl Chlorides and Bromides under Solvent-Free Conditions
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Solvent-free protocols for Miyaura borylation and the one-pot, two-step homocoupling of aryl halides are reported for the first time. Bis(dibenzylideneacetone)palladium(0) [Pd(dba)2] is an optimal source of palladium for Miyaura borylation, while for one-pot two-step homocoupling palladium(II) acetate [Pd(OAc)2] gives highest yields. Aryl bromides are coupled most efficiently using the DPEphos ligand. Chlorides are coupled using XPhos. The developed protocols are robust, versatile and easily reproducible on a large scale.
- Dzhevakov, Pavel B.,Topchiy, Maxim A.,Zharkova, Daria A.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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p. 977 - 983
(2016/04/05)
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- As tyrosine kinase inhibitors substituted indolinone derivatives
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The invention belongs to the technical field of a medicine, and particularly relates to a substituted indole ketone derivative as a tyrosine kinase inhibitor shown in a general formula (I), a pharmaceutically acceptable salt, a deuterated article or a stereoisomer thereof, wherein R1, R2, R3, R4, R5, R6, R7, R8, Ra, Rb, Rc, Rd, n, n1, n2, n3, n4, a ring A and a ring B are defined in the specification. The invention also relates to a preparation method of the compound, a drug preparation containing the compound, and application of the compound in preparation of a drug for preventing or treating a fibrosis disease and treating an excessive hyperplasia disease.
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Paragraph 0320-0322
(2016/10/24)
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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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p. 7082 - 7099
(2015/05/05)
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- Boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with silylborane and an alkoxy base: expanded scope and mechanistic studies
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A transition-metal-free method has been developed for the boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with a silylborane in the presence of an alkali-metal alkoxide. The base-mediated boryl substitution of organohalides with a silylborane was recently reported to provide the corresponding borylated products in good to high yields, and exhibit good functional group compatibility and high tolerance to steric hindrance. In this study, the scope of this transformation has been extended significantly to include a wide variety of functionalized aryl-, heteroaryl- and alkenyl halides. In particular, the boryl substitution of (E)- and (Z)-alkenyl halides proceeded smoothly to afford the corresponding alkenyl boronates in good to high yields with retention of the configuration using modified reaction conditions. The results of the mechanistic studies suggest that this boryl substitution proceeds via a carbanion-mediated mechanism.
- Yamamoto, Eiji,Ukigai, Satoshi,Ito, Hajime
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p. 2943 - 2951
(2015/06/17)
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- Palladium(ii)-catalysed ortho-arylation of N-benzylpiperidines
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PdII-catalysed ortho-arylation of benzylic heterocycles with arylboronic acid pinacol esters (Ar-BPin) via directed C-H bond activation to generate the desired biaryl products is reported. This methodology is efficient and applicable to a wide range of functionalised Ar-BPin and benzylic heterocycles, allowing the direct synthesis of important biaryl motifs in modest to good yield. This journal is
- Tan, Peng Wen,Haughey, Maxwell,Dixon, Darren J.
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supporting information
p. 4406 - 4409
(2015/03/18)
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- Palladium-Catalyzed Monofluoromethylation of Arylboronic Esters with Fluoromethyl Iodide
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The first palladium-catalyzed direct monofluoromethylation of arylboronic esters to produce monofluoromethyl arenes is reported. The reaction is typically carried out at room temperature within 4 h and has a good functional group tolerance. The monofluoromethylating agent, CH2FI, was readily prepared via a halogen-exchange process.
- Hu, Jingyu,Gao, Bing,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
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supporting information
p. 3086 - 3089
(2015/06/30)
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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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supporting information
p. 1702 - 1705
(2014/03/21)
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- Methanol-promoted borylation of arylamines: A simple and green synthetic method to arylboronic acids and arylboronates
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A Sandmeyer borylation of arylamines via a SN2Ar pathway promoted by methanol with sodium nitrite and hydrochloric acid as diazotization agent has been developed, which provide a simple and green synthetic method to arylboronic acids and arylboronates. Georg Thieme Verlag Stuttgart New York.
- Zhao, Cong-Jun,Xue, Dong,Jia, Zhi-Hui,Wang, Chao,Xiao, Jianliang
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supporting information
p. 1577 - 1584
(2014/07/08)
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- Synthesis of trimethylstannyl arylboronate compounds by sandmeyer-type transformations and their applications in chemoselective cross-coupling reactions
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A synthetic method based on Sandmeyer-type reactions to access both tin- and boron-substituted arenes from nitroaniline derivatives is described. This transformation can be applied to the synthesis of a series of functionalized trimethylstannyl arylboronates. In addition, the chemoselective reaction of the Stille and Suzuki-Miyaura cross-coupling reactions is explored, and a series of m- and p-terphenyl derivatives have been synthesized by conducting consecutive one-pot Stille and Suzuki-Miyaura cross-coupling reactions.
- Qiu, Di,Wang, Shuai,Tang, Shengbo,Meng, He,Jin, Liang,Mo, Fanyang,Zhang, Yan,Wang, Jianbo
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p. 1979 - 1988
(2014/04/03)
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- PPh3-mediated borylation of arenediazonium salts with bis(pinacolato)diborane
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A metal-free, PPh3-mediated borylation reaction of arenediazonium salts with bis(pinacolato)diborane has been developed under mild conditions. The process provides an attractive alternative to the traditional preparation of arylboronates, albeit in moderate yields.
- Chen, Shuangshuang,Pan, Zhangjin,Wang, Yan
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p. 982 - 986
(2015/06/16)
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- Convenient synthesis of arylboronates through a synergistic Pd/Cu-catalyzed miyaura borylation reaction under atmospheric conditions
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A highly efficient and practical borylation reaction of aryl iodides with bis(pinacolato)diboron has been established. By using Pd(OAc)2, CuI, and PPh3 as a ligand at room temperature under air in the presence of Cs2CO3, the protocol proved to be general. Various functionalized arylboronates were obtained in moderate to excellent yields. In addition, a possible reaction mechanism was proposed. An efficient borylation reaction of aryl iodides with bis(pinacolato)diboron is developed by using Pd(OAc)2 and CuI. This catalytic system has high catalytic efficiency at room temperature in air and functional-group tolerance for a wide range of substrates. Copyright
- Ratniyom, Jadsada,Dechnarong, Nattanee,Yotphan, Sirilata,Kiatisevi, Supavadee
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supporting information
p. 1381 - 1385
(2014/03/21)
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- Convenient Synthesis of Arylboronates through a Synergistic Pd/Cu-Catalyzed Miyaura Borylation Reaction under Atmospheric Conditions
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A highly efficient and practical borylation reaction of aryl iodides with bis(pinacolato)diboron has been established. By using Pd(OAc)2, CuI, and PPh3 as a ligand at room temperature under air in the presence of Cs2CO3, the protocol proved to be general. Various functionalized arylboronates were obtained in moderate to excellent yields. In addition, a possible reaction mechanism was proposed.
- Ratniyom, Jadsada,Dechnarong, Nattanee,Yotphan, Sirilata,Kiatisevi, Supavadee
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supporting information
p. 1381 - 1385
(2015/10/05)
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- Bipyridine periodic mesoporous organosilica: A solid ligand for the iridium-catalyzed borylation of C-H bonds
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With the goal to obtain a molecularly defined iridium(I) heterogeneous C-H functionalization catalyst, a periodic mesoporous organosilica (PMO) containing bipyridylene moieties in a matrix of biphenylene units as ligand platform was designed and fully characterized. The material exhibits a high surface area with small mesopores in a vermicular arrangement, and the pore walls show a highly crystal-like character. After surface passivation with chlorotrimethylsilane and functionalization with chloro(1,5-cyclooctadiene)iridium(I) dimer [{IrCl(COD)}2] a molecularly defined Ir(I) surface complex was obtained according to EXAFS and UV-Vis spectroscopy. This functionalized material catalyzes the direct C-H borylation of arenes to yield the corresponding boronic esters and can be reused without significant loss of activity.
- Gruening, Wolfram R.,Siddiqi, Georges,Safonova, Olga V.,Coperet, Christophe
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supporting information
p. 673 - 679
(2014/04/03)
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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 56-57
(2014/02/15)
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- SiliaCat diphenylphosphine palladium(II) catalyzed borylation of aryl halides
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We investigate the heterogeneously catalyzed direct synthesis of boronic acid pinacol esters using a wide range of aryl chlorides, bromides, and iodides, and bis(pinacolato)diboron as the borylating agent over the sol-gel entrapped SiliaCat diphenylphosphine palladium(II) catalyst. Optimization of the reaction conditions, scale-up of the optimized process, and analysis of palladium leaching enabled us to establish a new selective route for direct access to a diverse set of boronic acid pinacol esters. Clean borylation for scale-up: With the easy access and broad availability of diverse borylated species, the Suzuki-Miyaura reaction has become routine in industry and in research labs. We report a new selective route for direct access to a diverse set of boronic acid pinacol esters over the sol-gel entrapped SiliaCat diphenylphosphine palladium(II) catalyst that can be easily scaled-up.
- Pandarus, Valerica,Marion, Olivier,Gingras, Genevieve,Beland, Francois,Ciriminna, Rosaria,Pagliaro, Mario
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p. 1340 - 1348
(2014/05/20)
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- Gorlos-Phos for palladium-catalyzed borylation of aryl chlorides
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Using a readily available form of the mono-phosphine ligand, Gorlos-Phos·HBF4, Pd-catalyzed borylation of aryl chlorides afforded aryl boronates in high yields. A variety of functional groups are well compatible with this palladium catalyzed borylation reaction. This journal is the Partner Organisations 2014.
- Li, Pengbin,Fu, Chunling,Ma, Shengming
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p. 3604 - 3610
(2014/06/09)
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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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- Sandmeyer-type reaction to pinacol arylboronates in water phase: A green borylation process
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Copper(I)-catalyzed cross-coupling reactions of aryl diazonium salts with bis(pinacolato)diboron can proceed smoothly in the water phase at room temperature to give the corresponding arylboronate esters in good to high yields. The Sandmeyer-type borylation not only provides direct access to arylboronates bearing halo and acidic substituents, but also achieves a green borylation process. Georg Thieme Verlag Stuttgart · New York.
- Zhang, Jie,Wang, Xiaolong,Yu, Haitao,Ye, Jiahai
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experimental part
p. 1394 - 1396
(2012/06/30)
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- Flow synthesis of arylboronic esters bearing electrophilic functional groups and space integration with Suzuki-Miyaura coupling without intentionally added base
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We found that an integrated flow microreactor system enables the preparation of boronic esters bearing electrophilic functional groups using organolithium chemistry and that it allows for their use in Suzuki-Miyaura cross-coupling without intentionally added base. Based on this method, cross-coupling of two aryl halides bearing electrophilic functional groups was accomplished to obtain the corresponding biaryl compounds in one flow.
- Nagaki, Aiichiro,Moriwaki, Yuya,Yoshida, Jun-Ichi
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supporting information
p. 11211 - 11213
(2013/01/15)
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- Palladium nanoparticle catalysis: Borylation of aryl and benzyl halides and one-pot biaryl synthesis via sequential borylation-Suzuki-Miyaura coupling
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Palladium nanoparticles generated in PEG catalyze the reaction of bis(pinacolato)diboron with various aryl/benzyl halides to afford aryl/benzyl boronates in high yield. Arylboronates thus prepared, have been directly used in the Suzuki-Miyaura coupling reaction with different aryl halides and benzyl halides in a convenient one-pot, two-step solvent free green synthesis of unsymmetrical biaryls and diarylmethanes. The Royal Society of Chemistry 2012.
- Bej, Ansuman,Srimani, Dipankar,Sarkar, Amitabha
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experimental part
p. 661 - 667
(2012/05/04)
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