- Synthesis and catalytic activity of nickel(II) complexes containing NCN pincer ligands
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In this study, nickel(II) complexes [LmeNi(II)Cl]+(BPh4)?, [LmeNi(II)Cl]+(PF6)? and [Let2Ni(II)]+(BPh4)?2 were synthesised and characterized in the solution and solid states. Ligands Lme (C11H12N6) and Let (C13H17N6) featured a central carbene donor linked to pendant pyrazoles via either methylene or ethylene linkers. The catalytic activity of all three complexes was tested in the Kumada cross coupling reaction between phenylmagnesium bromide and aromatic halogen substituted substrates. [LmeNi(II)Cl]+(BPh4)?was found to be the most active catalyst.
- Nair, Ashwin G.,McBurney, Roy T.,Gatus, Mark R.D.,Walker, D.Barney,Bhadbhade, Mohan,Messerle, Barbara A.
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Read Online
- The photochemistry of polyhaloarenes XIII. The photohydrodehalogenation of 3,4-dibromobiphenyl
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Irradiation of 3,4-dibromobiphenyl (BpBr2) in acetonitrile resulted in the formation of 4-bromobiphenyl (BpBr) and 3- bromobiphenyl (3-BpBr) in a ratio of 7.6 ± 0.1 up to 22% conversion of starting material. The dependence of the reciprocal of the quantum yield (1/Φ) upon 1/BpBr2 is linear. Reduction of BpBr2 with lithium di-tert-butylbiphenylide generates a 3.6:1.0 ratio of BpBr to 3-BpBr, while photohydrodebromination of BpBr2 in the presence of triethylamine produces a similar ratio of 1.8:1.0. Product determining radical stability was assessed by radical debromination of BpBr2 using Ph3SnH in THF, which resulted in a BpBr:3-BpBr ratio of 1.5:1.0 AMI calculations on the product determining radicals provide the basis for rationalization of products via excimer and radical anion intermediates.
- Freeman, Peter K.,Jang, Jung-Suk,Haugen, Christian M.
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Read Online
- Synthesis, Structure, and Chiroptical Properties of Indolo- and Pyridopyrrolo-Carbazole-Based C2-Symmetric Azahelicenes
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Treatment of 11,12-bis(1,1’-biphenyl-3-yl or 6-phenylpyridin-2-yl)-substituted 11,12-dihydro-indolo[2,3-a]carbazole with an oxidizing system of Pd(II)/Ag(I) induced effective double dehydrogenative cyclization to afford the corresponding π-extended azahelicenes. The optical resolutions were readily achieved by a preparative chiral HPLC. It was found that the pyridopyrrolo-carbazole-based azahelicene that contains four nitrogen atoms exhibits ca. 6 times larger dissymmetry factors both in circularly dichroism (CD) and circularly polarized luminescence (CPL), |gCD| and |gCPL| values being 1.1×10?2 and 4.4×10?3, respectively, as compared with the parent indolocarbazole-based azahelicene. Theoretical calculations at the RI-CC2 level were employed to rationalize the observed enhanced chiroptical responses. The (chir)optical properties of the former helicene was further tuned by a protonation leading to remarkable red-shift with a considerable enhancement of the |gCPL| value.
- Taniguchi, Taisei,Nishii, Yuji,Mori, Tadashi,Nakayama, Ken-ichi,Miura, Masahiro
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supporting information
p. 7356 - 7361
(2021/04/26)
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- Facile synthesis of NC(sp3)O pincer palladium complexes and their use as efficient catalysts for Suzuki-Miyaura reaction of aryl bromides in aqueous medium
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Two NC(sp3)O pincer palladium(II) complexes 3a-3b were readily prepared in high yields in only two steps. Of the first step, catalytic hydrophosphination of 2-alkenoylpyridines and subsequent in situ phosphine oxidation produced the NC(sp3)O pincer preligands 2a-2b. The second step is palladation of the preligands 2a-2b where PdCl2 was used as the Pd source to afford the desired Pd pincers 3a-3b via C(sp3)-H bond activation. Single crystal X-ray diffraction analysis of complex 3a unambiguously confirmed the NCO tridentate coordination mode of the complexes. The two complexes 3a-3b were applied to catalyze the Suzuki-Miyaura reaction. Complex 3b was found to be more efficient and exhibited very high activity in the Suzuki reaction of structurally diverse aryl bromides with arylboronic acids in aqueous ethanol under air. At a reaction temperature of 70 °C, a TON of up to 1.9 × 105 and a TOF of up to 9800 h?1 were achieved. At lower temperatures 3b was still very active, giving a TON of up to 9.5 × 103 and a TOF of up to 3900 h?1 at room temperature.
- Gong, Jun-Fang,Li, Nan,Pan, Ya-Ping,Song, Mao-Ping,Yang, Jing-Jing,Zhu, Zhi-Wu
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- METHOD OF PRODUCING HALOGEN COMPOUND
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PROBLEM TO BE SOLVED: To provide a method of efficiently producing an aromatic compound including a halogen group of interest. SOLUTION: A method of producing a halogen compound represented by the specified general formula (1) comprises reacting a compound represented by the specified general formula (2) with a compound represented by the specified general formula (3) in the presence of a transition metal compound, a phosphine compound being 1,1'-bis(diphenylphosphino)ferrocene or 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene, and a base. (In the formula, Ar1 and Ar2 represent organic groups; X represents a halogen group; Z represents a halogen group different than X; m represents an integer greater than or equal to 0; p represents an integer greater than or equal to 1; and each R represents a hydrogen atom, alkyl group or phenyl group, where the two R's may be linked together to form a ring.) SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0052-0060
(2021/05/07)
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- Switching from biaryl formation to amidation with convoluted polymeric nickel catalysis
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A stable, reusable, and insoluble poly(4-vinyl-pyridine) nickel catalyst (P4VP-NiCl2) was prepared through the molecular convolution of poly(4-vinylpyridine) (P4VP) and nickel chloride. We proposed a coordination structure of the Ni center in the precatalyst based on elemental analysis and Ni K-edge XANES, and we confirmed that it is consistent with Ni K-edge EXAFS. The Suzuki?Miyaura-type coupling of aryl halides and arylboronic esters proceeded using P4VP-NiCl2 (0.1 mol % Ni) to give the corresponding biaryl compounds in up to 94% yield. Surprisingly, when the same reaction of aryl halides and arylboronic acid/ester was carried out in the presence of amides, the amidation proceeded predominantly to give the corresponding arylamides in up to 99% yield. In contrast, the reaction of aryl halides and amides in the absence of arylboronic acid/ester did not proceed. P4VP-NiCl2 successfully catalyzed the lactamization for preparing phenanthridinone. P4VP-NiCl2 was reused five times without significant loss of catalytic activity. Pharmaceuticals, natural products, and biologically active compounds were synthesized efficiently using P4VPNiCl2 catalysis. Nickel contamination in the prepared pharmaceutical compounds was not detected by ICP-MS analysis. The reaction was scaled to multigrams without any loss of chemical yield. Mechanistic studies for both Suzuki?Miyaura and amidation were performed.
- Sen, Abhijit,Dhital, Raghu N.,Sato, Takuma,Ohno, Aya,Yamada, Yoichi M.A.
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p. 14410 - 14418
(2020/12/21)
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- Arylation of aryllithiums with: S-arylphenothiazinium ions for biaryl synthesis
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Aryllithiums are one of the most common and important aryl nucleophiles; nevertheless, methods for arylation of aryllithums to produce biaryls have been limited. Herein, we report arylation of aryllithiums with S-arylphenothiazinium ions through selective
- Morofuji, Tatsuya,Yoshida, Tatsuki,Tsutsumi, Ryosuke,Yamanaka, Masahiro,Kano, Naokazu
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p. 13995 - 13998
(2020/11/21)
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- Organocatalyst in Direct C(sp2)-H Arylation of Unactivated Arenes: [1-(2-Hydroxyethyl)-piperazine]-Catalyzed Inter-/Intra-molecular C-H Bond Activation
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This article describes the identification of 1-(2-hydroxyethyl)-piperazine as a new, cost-effective, highly efficient organocatalyst, which promotes both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in the presence of potassium tert-butoxide. While the inter-molecular C-H arylation of unactivated benzenes with aryl halides (Ar-X; X = I, Br, Cl) toward biaryl syntheses underwent smoothly in the presence of only 10 mol percent organocatalyst, the intra-molecular C-H arylation catalytic system composed of 40 mol percent each of the catalyst and the additive (4-dimethylaminopyridine (DMAP)). The novel catalyst was also able to perform both inter- A nd intra-molecular direct arylations simultaneously in a single pot. The mechanistic studies confirmed the involvement of aryl radical anions and proceeded via a single-electron-transfer (SET) mechanism. The large substrate scope, high functional group tolerance, competition experiments, gram-scale synthesis, and kinetic studies further highlight the importance and versatile nature of the methodology as well as the compatibility of the new catalyst. To the best of our knowledge, this is the first report on any organocatalyst that reported detailed investigations of both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in a single representation.
- Yadav, Lalit,Tiwari, Mohit K.,Shyamlal, Bharti Rajesh Kumar,Chaudhary, Sandeep
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p. 8121 - 8141
(2020/07/16)
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- Palladium (II)–Salan Complexes as Catalysts for Suzuki–Miyaura C–C Cross-Coupling in Water and Air. Effect of the Various Bridging Units within the Diamine Moieties on the Catalytic Performance
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Water-soluble salan ligands were synthesized by hydrogenation and subsequent sulfonation of salens (N,N’-bis(slicylidene)ethylenediamine and analogues) with various bridging units (linkers) connecting the nitrogen atoms. Pd (II) complexes were obtained in reactions of sulfosalans and [PdCl4]2?. Characterization of the ligands and complexes included extensive X-ray diffraction studies, too. The Pd (II) complexes proved highly active catalysts of the Suzuki–Miyaura reaction of aryl halides and arylboronic acid derivatives at 80 ?C in water and air. A comparative study of the Pd (II)–sulfosalan catalysts showed that the catalytic activity largely increased with increasing linker length and with increasing steric congestion around the N donor atoms of the ligands; the highest specific activity was 40,000 (mol substrate) (mol catalyst × h)?1. The substrate scope was explored with the use of the two most active catalysts, containing 1,4-butylene and 1,2-diphenylethylene linkers, respectively.
- Bunda, Szilvia,Joó, Ferenc,Kathó, ágnes,Udvardy, Antal,Voronova, Krisztina
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supporting information
(2020/09/18)
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- Visible-Light-Promoted, Catalyst-Free Gomberg-Bachmann Reaction: Synthesis of Biaryls
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Biaryls were synthesized via a novel visible-light-promoted Gomberg-Bachmann reaction that does not require a photosensitizer or any metal reagents. The formation of an electron donor-acceptor complex between aryl diazonium salts and pyridine allows, under visible-light irradiation, the synthesis of biaryls in moderate-to-high yields.
- Lee, Juyoung,Hong, Boseok,Lee, Anna
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p. 9297 - 9306
(2019/08/12)
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- Palladium-catalysed room-temperature Suzuki–Miyaura coupling in water extract of pomegranate ash, a bio-derived sustainable and renewable medium
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An agro waste-derived, ‘water extract of pomegranate ash’ (WEPA), has been utilized for the first time as a renewable medium for Pd(OAc)2-catalysed Suzuki–Miyaura cross-coupling at room temperature. This method offers a simple and sustainable synthesis of biaryls from aryl halides and arylboronic acids under ligand- and external base-free aerobic and ambient conditions. This method has been found effective for both activated and unactivated aryl halides in the production of biaryls with moderate to nearly quantitative yields. The protocol shows high chemoselectivity over identical/similar reactive sites in aryl halides (i.e. selectivity over identical halogens or different halogens of aryl halides). This method exhibits high regioselectivity, i.e. the selective reactivity of a halogen over other identical halogens at different positions on the aromatic nucleus. Therefore, we disclose here a clean, benign, substantial chemo- and regioselective and highly economic alternative method for the palladium-assisted synthesis of biaryls using an agro waste-derived medium.
- Appa, Rama Moorhy,Prasad, S. Siva,Lakshmidevi, Jangam,Naidu, Bandameeda Ramesh,Narasimhulu, Manchala,Venkateswarlu, Katta
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- Synthesis of Bi(hetero)aryls via Sequential Oxidation and Decarboxylation of Benzylamines in a Batch/Fully Automated Continuous Flow Process
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Catalytic dehydrogenative cross-coupling of two C–H bonds represents a green strategy in view of the atom- and step-economy. However, the challenge is to discover a new innovative bond strategy, especially for the direct coupling between Csp2–H
- Mahajan, Bhushan,Aand, Dnyaneshwar,Singh, Ajay K.
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supporting information
p. 2831 - 2835
(2018/06/21)
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- Direct Aryl-Aryl Coupling without Pre-Functionalization Enabled by Excessive Oxidation of Two-Electron Ag(I)/Ag(III) Catalyst
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Reported herein is a catalytic platform for formation of unsymmetrical biaryls by the coupling between inert Csp2?CH3 and Csp2?H via a tandem catalytic strategy. The platform utilizes traditional AgNO3 catalyst and excess amount of K2S2O8 oxidant. The excessive oxidant present converts the traditional one-electron Ag(I)/Ag(II) chemistry to two-electron Ag(I)/Ag(III) one, enabling one-pot synthesis of aryl-aryl scaffolds by using unactivated cheap commodity chemicals. (Figure presented.).
- Singh, Ajay K.,Kim, Min-Gyu,Lee, Hyune-Jea,Singh, Rakhi,Cho, Seung Hwan,Kim, Dong-Pyo
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supporting information
p. 2032 - 2042
(2018/04/11)
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- Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes
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Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes are described. This redox neutral strategy offers an efficient approach to diverse biaryls, vinyl arenes and arylacetylenes. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the in situ formation of Ph3PAuIR (R = aryl, vinyl and alkynyl) species which is crucial for the activation of aryldiazonium salts.
- Akram, Manjur O.,Shinde, Popat S.,Chintawar, Chetan C.,Patil, Nitin T.
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supporting information
p. 2865 - 2869
(2018/05/03)
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- RORγ MODULATORS
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The invention provides an RORγ receptor agonist comprising a compound of formula (I), wherein the variables are as defined herein. These compounds are analogous to known RORγ receptor antagonists. The invention further provides a method of activating -the nuclear receptor RORγ, comprising -contacting the RORγ with an effective amount or concentration of a compound of the invention; and a method of treating cancer in a patient, comprising administering to the patient an effective dose of a compound of the invention.
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Page/Page column 57
(2018/04/13)
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- A Sustainable Heterogeneous Iron Catalyst Fe/SBA-15 towards Direct Arylation of Unactivated C(sp3)?H and C(sp2)?H Bonds with Arenes
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Iron grafted over mesoporous silica (8 wt %Fe/SBA-15) is a sustainable, efficient heterogeneous iron catalyst for direct arylation of biphenyl methane C(sp3)?H and benzene C(sp2)?H bonds. The selective extraction deposition (SED) technique was adopted to graft iron easily over the mesoporous support SBA-15 by using LaFeO3 as an iron precursor. The synthesized catalyst has been characterized by EPR spectroscopy, diffuse reflectance UV/Vis spectroscopy, and temperature programmed reduction (TPR) analysis to understand the coordination environment and state of oxidic iron species grafted over the mesoporous SBA-15. TPR results confirm the presence of isolated, clustered, oligomeric oxidic iron species in the catalyst. The adopted SED technique is highly successful for grafting 8 wt % iron into the mesopores of SBA-15 without forming iron oxide particles. Unlike homogeneous iron, the 8 wt %Fe/SBA-15 catalyst does not need support from an electron-withdrawing group and additives to carry out arylation of benzene and could be successfully recycled five times.
- Rajendran,Satishkumar
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p. 1284 - 1291
(2017/04/14)
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- ONE STEP DIRECT ARYLATION OF COMMODITY CHEMICALS TO SPECIALTY CHEMICALS BY TANDEM CATALYTIC PLATFORM
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The present invention relates to a continuous direct arylation process based on a tandem catalyst for synthesizing specialty chemicals. A method for synthesizing an aryl-aryl structure from a substrate selected from the group consisting of benzyl alcohol, benzyl amine and toluene which are low value added compounds is developed using a silver ion-containing tandem catalyst. The method is applied for synthesizing hexaphenyl arylene and can be applied for synthesizing high value added compounds (not only natural substances and chemical compounds but pharmaceutical and agricultural pesticide relative fields) directly from primary raw materials through the reaction.COPYRIGHT KIPO 2017
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Paragraph 0057; 0058; 0066-0103; 0106
(2018/02/28)
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- Direct arylation of inactivated benzene with aryl acyl peroxides toward biaryls
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A direct arylation of inactivated benzene with acyl peroxides was developed, affording biaryls in good to excellent yields. This transformation underwent a radical pathway under metal-free, base-free and additive-free conditions with good functional group compatibility.
- Pan, Changduo,Zhu, Jiawei,Chen, Rongzhen,Yu, Jin-Tao
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supporting information
p. 6467 - 6469
(2017/08/16)
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- Arylation of hydrocarbons enabled by organosilicon reagents and weakly coordinating anions
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Over the past 80 years, phenyl cation intermediates have been implicated in a variety of C-H arylation reactions. Although these examples have inspired several theoretical and mechanistic studies, aryl cation equivalents have received limited attention in organic methodology. Their high-energy, promiscuous reactivity profiles have hampered applications in selective intermolecular processes. We report a reaction design that overcomes these challenges. Specifically, we found that b-silicon-stabilized aryl cation equivalents, generated via silylium-mediated fluoride activation, undergo insertion into sp3 and sp2 C-H bonds. This reaction manifold provides a framework for the catalytic arylation of hydrocarbons, including simple alkanes such as methane. This process uses low loadings of Earth-abundant initiators (1 to 5 mole percent) and occurs under mild conditions (30° to 100°C).
- Shao, Brian,Bagdasarian, Alex L.,Popov, Stasik,Nelson, Hosea M.
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- Mild, visible light-mediated decarboxylation of aryl carboxylic acids to access aryl radicals
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Herein we present the first example of aryl radical formation via the visible light-mediated decarboxylation of aryl carboxylic acids using photoredox catalysis. This method constitutes a mild protocol for the decarboxylation of cheap and abundant aryl carboxylic acids and tolerates both electron-rich substrates and those lacking ortho-substitution. The in situ formation of an acyl hypobromite is proposed to prevent unproductive hydrogen atom abstraction and trapping of the intermediate aroyloxy radical, enabling mild decarboxylation.
- Candish,Freitag,Gensch,Glorius
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p. 3618 - 3622
(2017/07/11)
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- Synthetic method of directly coupling aryl halide by aromatic hydrocarbon Grignard reagent in the presence of recycled modified palladium-charcoal
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The invention provides a synthetic method of directly coupling aryl halide by an aromatic hydrocarbon Grignard reagent. The synthetic method includes performing reflux and water separation of a catalyst Pd/C and an azeotropic organic solvent of non-halogenated hydrocarbon and water, adding an organic phosphine ligand, performing a complexation reaction to obtain a catalyst organic phosphine ligand complexing Pd/C, using aryl halide as an initial material, performing a Grignard reaction at 10-90 DEG C to obtain a Grignard reagent, adding the catalyst, performing a coupled reaction of aryl halide and the Grignard reagent to obtain a coupling aromatic hydrocarbon. The synthetic method uses one-step method, has low synthesis cost, is green and environmental friendly, and is a high-efficiency and clean synthetic technology of coupling aryl halide.
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Paragraph 0019; 0020; 0021
(2016/10/08)
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- N-Arylsulfonyl Indolines as Retinoic Acid Receptor-Related Orphan Receptor γ (RORγ) Agonists
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The nuclear retinoic acid receptor-related orphan receptor γ (RORγ; NR1F3) is a key regulator of inflammatory gene programs involved in T helper 17 (TH17) cell proliferation. As such, synthetic small-molecule repressors (inverse agonists) targeting RORγ have been extensively studied for their potential as therapeutic agents for various autoimmune diseases. Alternatively, enhancing TH17 cell proliferation through activation (agonism) of RORγ may boost an immune response, thereby offering a potentially new approach in cancer immunotherapy. Herein we describe the development of N-arylsulfonyl indolines as RORγ agonists. Structure–activity studies reveal a critical linker region in these molecules as the major determinant for agonism. Hydrogen/deuterium exchange coupled to mass spectrometry (HDX-MS) analysis of RORγ–ligand complexes help rationalize the observed results.
- Doebelin, Christelle,Patouret, Rémi,Garcia-Ordonez, Ruben D.,Chang, Mi Ra,Dharmarajan, Venkatasubramanian,Kuruvilla, Dana S.,Novick, Scott J.,Lin, Li,Cameron, Michael D.,Griffin, Patrick R.,Kamenecka, Theodore M.
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supporting information
p. 2607 - 2620
(2016/12/09)
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- Ligand-controlled chemoselectivity in potassium tert-amylate-promoted direct C-H arylation of unactivated benzene with aryl halides
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Direct C-H arylation of unactivated benzene with aryl halides under various simple ligands (EDA, DMEDA, ethylene glycol, etc.) in the presence of potassium tert-amylate (t-AmOK) base at mild temperature (80 °C) have been developed. This transition-metal-free radical cross-coupling offers an efficient way to synthesize various biaryls in good yields through base-promoted homolytic aromatic substitution. And mechanistic investigations have provided insight into the chemoselectivity of couplings between haloiodobenzenes and benzene and showed that phenanthroline and its derivatives not only initiate these radical reactions like most of other ligands (EDA, DMEDA, ethylene glycol, etc.), but also participate in the electron transfer process of biaryl radical anion intermediates.
- Liu, Wei,Xu, Lige
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p. 4974 - 4981
(2015/06/25)
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- Synthesis of Biaryls via Benzylic C-C Bond Cleavage of Styrenes and Benzyl Alcohols
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A metal-free oxidative coupling of styrenes and benzyl alcohols with arenes has been developed for the synthesis of biaryls. The reaction features a conspicuous benzylic C-C bond cleavage of styrenes and benzyl alcohols. The reaction with both substrates proceeds through a common aldehydic intermediate formed through oxidative C-C bond cleavage of alkene and oxidation of benzyl alcohols. The reaction proceeds efficiently over a broad range of substrates with excellent functional group tolerance.
- Kumar, Arvind,Shah, Bhahwal Ali
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supporting information
p. 5232 - 5235
(2015/11/18)
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- Copper/Selectfluor-System-Catalyzed Dehydration-Oxidation of Tertiary Cycloalcohols: Access to β-Substituted Cyclohex-2-enones, 4-Arylcoumarins, and Biaryls
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A route to β-substituted cyclohex-2-enones, 4-arylcoumarins, and biaryls has been developed. This approach involves a one-pot Cu0/Selectfluor-catalyzed dehydration-oxidation of tertiary cycloalcohols. Thus, by using 2 equiv. of Selectfluor at 25 C, the dehydration-oxidation of tertiary cyclohexanols and oxabenzocyclohexanols gave β-substituted cyclohex-2-enones and 4-arylcoumarins, respectively; whereas the dehydration-oxidation of tertiary cyclohexanols gave biaryls as the final products by using 2.5 equiv. of Selectfluor at 80 C. A route to β-substituted cyclohex-2-enones, 4-arylcoumarins, and biaryls has been developed. This approach involves a one-pot Cu0/Selectfluor-catalyzed dehydration-oxidation of tertiary cycloalcohols.
- Ren, Shaobo,Zhang, Jian,Zhang, Jiahui,Wang, Heng,Zhang, Wei,Liu, Yunkui,Liu, Miaochang
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supporting information
p. 5381 - 5388
(2015/08/24)
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- Pd-catalyzed desulfitative and denitrogenative Suzuki-type reaction of arylsulfonyl hydrazides
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A palladium-catalyzed desulfitative-denitrogenative coupling of arylsulfonyl hydrazides and arylboronic acids with the assistance of catalytic ligands is described. The reaction showed very good selectivity and tolerated a wide range of functionalities without the aid of expensive copper- or silver-based stoichiometric co-oxidants. We have successfully applied this new cross-coupling reaction to the synthesis of terphenyls and OTBN.
- Zhong, Shuangling,Sun, Chenggang,Dou, Sen,Liu, Wencong
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p. 27029 - 27033
(2015/03/30)
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- Silver-catalyzed arylation of (hetero)arenes by oxidative decarboxylation of aromatic carboxylic acids
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A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods.
- Kan, Jian,Huang, Shijun,Lin, Jin,Zhang, Min,Su, Weiping
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supporting information
p. 2199 - 2203
(2015/02/19)
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- LIGHT-EMITTING MATERIAL FOR ORGANIC ELECTROLUMINESCENT DEVICE, ORGANIC ELECTROLUMINESCENT DEVICE USING SAME, AND MATERIAL FOR ORGANIC ELECTROLUMINESCENT DEVICE
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In the present invention, disclosed are a novel aromatic compound with outstanding light-emitting efficiency and heat stability, a manufacturing method thereof and an organic electronic device including the novel aromatic compound. For this, in the present invention, provided are a ring-formed aromatic compound and a novel aromatic amine derivative denoted by chemical formula 1 for improving performance of the device.COPYRIGHT KIPO 2015
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Paragraph 0167-0169
(2016/10/17)
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- CONDENSED CYCLIC COMPOUND, AND ORGANIC LIGHT EMITTING DEVICE INCLUDING THE SAME
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Disclosed are a condensed ring compound and an organic light emitting device comprising the condensed ring compound. The organic light emitting device comprises: a first electrode; a second electrode facing the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises the condensed ring compound.COPYRIGHT KIPO 2015
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Paragraph 1176
(2016/10/08)
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- Functionalized Phosphonium Ionic Liquids: Synthesis and Application
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A series of phosphonium salts with sterically hindered cation But3P+(CH2COOEt)X- (X = Cl, BF4, N(SO2CF3)2) (1) was prepared for the first time. Palladium nanoparticles (PdNPs) stabilized by (1) showed moderate activity as catalyst in Suzuki cross-coupling reaction of bromoarenes and phenylboronic acid.
- Arkhipova, Daria,Ermolaev, Vadim,Miluykov, Vasili,Nigmatullina, Lilia,Sinyashin, Oleg
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supporting information
p. 899 - 901
(2016/01/15)
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- Vasicine catalyzed direct C-H arylation of unactivated arenes: Organocatalytic application of an abundant alkaloid
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Vasicine, a quinazoline alkaloid isolated from Adhatoda vasica, has been employed as an organocatalyst for direct C-H arylation of unactivated arenes with aryl iodides/bromides without the assistance of any transition metal catalyst. A number of sensitive functional groups such as methyl, methoxy, O-benzyl, acetyl, and amino were well tolerated under present reaction conditions. Mechanistic investigation supported the involvement of radical intermediates.
- Sharma, Sushila,Kumar, Manoranjan,Kumar, Vishal,Kumar, Neeraj
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supporting information
p. 4868 - 4871
(2013/08/28)
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- 9H-CARBAZOLE COMPOUNDS AND ELECTROLUMINESCENT DEVICES INVOLVING THEM
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The present invention relates to a novel organic luminescent compound and an organic electroluminescent device containing the same. The compounds according to the present invention have high luminous efficiency and long operation lifetime. Therefore, they can produce an organic electroluminescent device having an improved power consumption.
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Paragraph 127-128
(2013/03/26)
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- Sustainable H2O/ethyl lactate system for ligand-free Suzuki-Miyaura reaction
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A sustainable catalyst system consisted of H2O/ethyl lactate (EL), Pd(OAc)2 and K2CO3 has been developed as a generally applicable protocol for Suzuki-Miyaura reactions using various aryl bromides and iodides to incorporate arylboronic acids under ligand-free conditions. This protocol is advantageous owing to the employment of water and non-toxic, biomass available ethyl lactate as green media. In addition, as a co-solvent with water, ethyl lactate displayed evident superiority over conventional polar organic solvents such as DMF, DMSO and dioxane etc., which implied the additional potential function of EL as a ligand in these reactions.
- Wan, Jie-Ping,Wang, Chunping,Zhou, Rihui,Liu, Yunyun
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p. 8789 - 8792
(2015/01/30)
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- Iron-catalyzed oxidative coupling of arylboronic acids with benzene derivatives through homolytic aromatic substitution
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Fe(OTf)3-1,10-phenanthroline catalyzes oxidative coupling of arylboronic acids with benzene derivatives using t-BuOOt-Bu as an oxidant. The reaction proceeds through homolytic aromatic substitution with aryl radicals generated from arylboronic acids and t-BuO.
- Uchiyama, Nanase,Shirakawa, Eiji,Nishikawa, Ryo,Hayashi, Tamio
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supporting information; experimental part
p. 11671 - 11673
(2011/12/05)
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- Base free aryl coupling of diazonium compounds and boronic esters: Self-activation allowing an overall highly practical process
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Boronic esters have long been considered as poor partners in cross-coupling reactions with arene diazoniums. Here is reported an unprecedented application of self-activated boronic esters in a base-free cross-coupling reaction with diazonium salts under mild and user friendly conditions.
- Bonin, Helene,Delbrayelle, Dominique,Demonchaux, Patrice,Gras, Emmanuel
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supporting information; experimental part
p. 2677 - 2679
(2010/07/08)
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- Suzuki-Miyaura, Mizoroki-Heck carbon-carbon coupling and hydrogenation reactions catalysed by PdII and RhI complexes containing cyclodiphosphazane cis-{tBuNP(OC6H4OMe-o)} 2
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The catalytic activity of the palladium complex cis-[PdCl 2{(tBuNP(OC6H4OMe-o)) 2-κP}2] (2) containing cis-{tBuNP(OC 6H4OMe-o)}2 (1) in Suzuki-Miyaura and Mizoroki-Heck carbon-carbon cross coupling reactions is described. The compound 2 also displays very high activity in Mizoroki-Heck coupling reactions. The rhodium(I) complex [RhCl(COD){(tBuNP(OC6H 4OMe-o))2-κP}] (3) acts as an excellent catalyst for the hydrogenation of several terminal olefins. Indian Academy of Sciences.
- Mohanty, Sasmita,Balakrishna, Maravanji S.
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experimental part
p. 137 - 142
(2010/11/17)
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- Manganese(III) acetate-mediated synthesis of biaryls under microwave irradiation
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Manganese(III) acetate (Mn(OAc)3)-mediated synthesis of biaryls and heterobiaryls starting from arylboronic acid was developed under microwave irradiation in high yields. Microwaves were also used for the synthesis of Mn(OAc)3 from KMnO4 and acetic acid. Additional irradiation of this in situ generated Mn(OAc)3 with arylboronic acids, which in turn furnished the biaryls in high yields in a one pot reaction. This is superior from the point of view of yield, short reaction time, sensitive functional group toleration, and more environmentally friendly than the reported methods with a minimum amount of benzene and thiophene as a reagent but not as a solvent.
- Demir, Ayhan S.,Findik, Hamide,Saygili, Nezire,Tuna Subasi
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experimental part
p. 1308 - 1312
(2010/04/04)
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- Structure-activity relationships comparing N-(6-methylpyridin-yl)- substituted aryl amides to 2-methyl-6-(substituted-arylethynyl)pyridines or 2-methyl-4-(substituted-arylethynyl)thiazoles as novel metabotropic glutamate receptor subtype 5 antagonists
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The metabotropic glutamate receptor subtype 5 (mGluR5) has been implicated in anxiety, depression, pain, mental retardation, and addiction. The potent and selective noncompetitive mGluR5 antagonist 2-methyl-6-(phenylethynyl)pyridine (MPEP, 1) has been a critically important tool used to further elucidate the role of mGluR5 in these CNS disorders. In an effort to provide novel and structurally diverse selective mGluR5 antagonists, we previously described a set of analogues with moderate activity wherein the alkyne bond was replaced with an amide group. In the present report, extended series of both amide and alkyne-based ligands were synthesized. MGluR5 binding and functional data were obtained that identified (1) several novel alkynes with comparable affinities to 1 at mGluR5 (e.g., 10 and 20-23), but (2) most structural variations to the amide template were not well tolerated, although a few potent amides were discovered (e.g., 55 and 56). Several of these novel analogues show drug-like physical properties (e.g., cLogP range = 2-5) that support their use for in vivo investigation into the role of mGluR5 in CNS disorders.
- Kulkarni, Santosh S.,Zou, Mu-Fa,Cao, Jianjing,Deschamps, Jeffrey R.,Rodriguez, Alice L.,Conn, P. Jeffrey,Newman, Amy Hauck
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experimental part
p. 3563 - 3575
(2010/04/05)
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- Iron-mediated direct arylation of unactivated arenes
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(Chemical Equation Presented) Inexpensive and straightforward: An iron-mediated cross-coupling reaction generates biaryl compounds through C-H bond activation, using easily handled reagents with low toxicity. Under the optimized reaction conditions a series of substituted phenylboronic acids were coupled with several simple unactivated arenes.
- Wen, Jun,Zhang, Ji,Chen, Shan-Yong,Li, Jing,Yu, Xiao-Qi
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supporting information; experimental part
p. 8897 - 8900
(2009/05/26)
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- Potassium permanganate/carboxylic acid/organic solvent: a powerful reagent for enone oxidation and aryl coupling reactions
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The α′-acetoxylation of enones and the α-acetoxylation of aromatic ketones were carried out with potassium permanganate and acetic acid, in which acetoxylation products were obtained in 74-96% yields. The same reaction was carried out with carboxylic acids other than acetic acid, which furnished corresponding acyloxy ketones with the same regioselectivity. For the first time, formyloxylation products were synthesized in a 61-85% yield by using formic acid. The potassium permanganate and acetic acid method was also used for aryl coupling reactions. The reaction of arylboronic acids and arylhydrazines in benzene with potassium permanganate and acetic acid in turn furnished biaryls in 85-96% yield. We have shown that potassium permanganate/carboxylic acid/organic solvent behaves as manganese(III) acetate.
- Demir, Ayhan S.,Findik, Hamide
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p. 6196 - 6201
(2008/09/21)
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- Tris(4-methylpiperazin-1-yl)phosphane, P(NC4H 8NMe)3: Synthesis, structural studies, group 10 and 11 metal complexes and catalytic investigations
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Group 10 and 11 metal complexes of a multidentate phosphorus-nitrogen donor ligand tris(4-methylpiperazin-1-yl)-phosphane, P(NC4H 8NMe)3 (1) are reported. The reactions of 1 with an equimolar amount of CuX (X = Cl, Br and I) afford tetranuclear cubane-like complexes [(CuX)-{P(NC4H8NMe)3}]4 (2, X = Cl; 3, X = Br and 4, X = I) in excellent yield. Treatment of 1 with AuCl(SMe2) produces a mononuclear complex, [(AuCl){P(NC 4H8NMe)3}] (5). Reaction of 1 with AgCN produces a 2D AgI polymeric sheet, [(AgCN)2-{P(NC4H 8NMe)3}]n (6) in moderate yield. The similar 1:1 reactions of 1 with AgX (X = Cl and Br) furnish dinuclear complexes, [(AgX){P(NC4H8NMe)3}]2 (7, X = Cl and 8, X = Br). The 2:1 reactions of 1 with [M(COD)Cl2] (M = Pd or Pt) afford [{P(NC4H8NMe)3}2MCl 2] (9, M = Pd and 10, M = Pt) in quantitative yield. The molecular structures of complexes 1-3 and 6 are established through single-crystal X-ray diffraction studies. The catalytic activity of the PdII complex 9 has been investigated in Suzuki cross coupling reactions. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Ganesamoorthy, Chelladurai,Mague, Joel T.,Balakrishna, Maravanji S.
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p. 596 - 604
(2008/12/22)
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- Soluble gold and palladium complexes heterogenized on MCM-41 are effective and versatile catalysts
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Chiral Schiff base-gold and -palladium complexes were immobilized on ordered mesoporous silica supports (MCM-41), and their catalytic hydrogenation ability is studied and compared with that of their homogeneous counterparts. The high accessibility introduced by the structure of the supports allows the preparation of highly efficient immobilized catalysts with TOFs of up to 6000 h-1 for the hydrogenation of diethyl itaconate. The easily recoverable immobilized catalysts duplicate the activity of their homogeneous analogues, and no deactivation of the catalysts is observed after repeated recycling. Gold(III) homogeneous or heterogenized complexes also catalyze the homocoupling of arylboronic acids or alkynes to afford symmetrical biaryls, whereas the respective gold(I) and palladium(II) complexes catalyze the corresponding cross-coupling reaction. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Gonzalez-Arellano, Camino,Corma, Avelino,Iglesias, Marta,Sanchez, Felix
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scheme or table
p. 1107 - 1115
(2009/02/05)
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- Short, facile, and high-yielding synthesis of extremely efficient pincer-type suzuki catalysts bearing aminophosphine substituents
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(Chemical Equation Presented) Feeling the pinch: Aryl bromides can be coupled with phenylboronic acid quantitatively within a few minutes by using pincer-type catalysts bearing aminophosphine substituents. [Pd(Cl) 2P(NR2)3] has been used as a template for the pincer core directly on the metal center (see scheme, NR2 = piperidinyl, X = NH or O), which makes the independent synthesis and purification of the air- and moisture-sensitive ligand systems unnecessary.
- Bolliger, Jeanne L.,Blacque, Olivier,Frech, Christian M.
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p. 6514 - 6517
(2008/09/16)
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- Aryl bromide/triflate selectivities reveal mechanistic divergence in palladium-catalysed couplings; the Suzuki-Miyaura anomaly
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In palladium-catalysed cross-coupling reactions, the outcome of competition between aryl bromides and aryl triflates depends on the nucleophilic partner; Suzuki couplings with R-B generally follow a different pattern from other R-M species. The Royal Society of Chemistry.
- Espino, Gustavo,Kurbangalieva, Almira,Brown, John M.
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p. 1742 - 1744
(2008/02/04)
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- Heterogenized gold(I), gold(III), and palladium(II) complexes for C-C bond reactions
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Recycling of heterogenized gold(I), gold(III), and palladium(II) complexes could be achieved for Suzuki and Sonogashira cross-coupling reaction between iodo benzene and arylboronic acids or alkynes. Au(I) and Pd(II) afford selectively nonsymmetrical biaryl compounds, while gold(III) complexes can only catalyze the arylboronic or alkynes homocoupling. Recycling occurs without loss of the catalytic activity after several reaction cycles. Georg Thieme Verlag Stuttgart.
- Corma, Avelino,González-Arellano, Camino,Iglesias, Marta,Pérez-Ferreras, Susana,Sánchez, Félix
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p. 1771 - 1774
(2008/02/07)
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- Enantioselective cyclopropanation with TADDOL-derived phosphate ligands
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The synthesis of new chiral TADDOL-derived phosphate ligands is described. The ligands were efficiently synthesized on a multi-gram scale in three steps starting from the readily available corresponding TADDOL and were fully characterized. An X-ray structure was obtained and compared to known BINOL-phosphates. Their use in the asymmetric Simmons-Smith cyclopropanation of both functionalized and unfunctionalized olefins gave the desired cyclopropanes in good yields and good to moderate enantioselectivities.
- Voituriez, Arnaud,Charette, Andre B.
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p. 2363 - 2370
(2007/10/03)
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- Synthesis of biaryls and polyaryls by ligand-free Suzuki reaction in aqueous phase
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A highly efficient palladium acetate-catalyzed ligand-free Suzuki reaction in aqueous phase was developed in short reaction times (0.5-1 h) at 35 °C in air. The key for such a successful catalytic system was the use of a suitable amount of cosolvents in the aqueous phase. The method could be extended to the consecutive multi-Suzuki coupling, and polyaryls were prepared in a single one-pot step in high selectivity and excellent yield under mild reaction conditions (60 °C).
- Liu, Leifang,Zhang, Yuhong,Xin, Bingwei
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p. 3994 - 3997
(2007/10/03)
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- Solid-phase synthesis with resin-bound triarylbismuthanes: Traceless and multidirectional cleavage of unsymmetrical biphenyls
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A multistep solid-phase organic synthesis with resin-bound bismuth linker is described. The flexibilities inherent in this system through novel chemoselective cross-coupling reactions, in conjunction with multidirectional and/or traceless cleavage methodologies, are exploited.
- Rasmussen, L. Kyhn,Begtrup, Mikael,Ruhland, Thomas
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p. 1230 - 1232
(2007/10/03)
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- Gold (I) and (III) catalyze Suzuki cross-coupling and homocoupling, respectively
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Trinuclear triphenylphosphine 1,2Au(I) complexes with the [N,N,O]-tridentate unsymmetrical Schiff bases (1,2) catalyze the Suzuki cross-coupling reaction to afford nonsymmetrical biaryls in good yields, whereas the 1,2Au(III) complexes give only arylboronic homocoupling.
- Gonzalez-Arellano,Corma,Iglesias,Sanchez
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p. 497 - 501
(2007/10/03)
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- Exploiting a basic chemosensitizing pharmacophore hypothesis. Part 1: Synthesis and biological evaluation of novel arylbromide and bicyclic chemosensitizers against drug-resistant malaria parasites
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An exploratory series of novel arylbromide and bicyclic chemosensitizers (modulators) against chloroquine-resistant Plasmodium falciparum were designed and synthesized on the basis of a basic chemosensitizing pharmacophore hypothesis in malaria. ortho-Substituted bromo and biphenyl ether compounds displayed the best activity from the series.
- Chouteau, Franck,Ramanitrahasimbola, David,Rasoanaivo, Philippe,Chibale, Kelly
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p. 3024 - 3028
(2007/10/03)
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- Structure-activity relationship of triaryl propionic acid analogues on the human EP3 prostanoid receptor
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Potent and selective ligands for the human EP3 prostanoid receptor are described. Triaryl compounds bearing an ortho-substituted propionic acid moiety were identified as potent EP3 antagonists based on the SAR described herein. The binding affinities of key compound on all eight human prostanoid receptors is reported.
- Gallant, Michel,Belley, Michel,Carriere, Marie-Claude,Chateauneuf, Anne,Denis, Danielle,Lachance, Nicolas,Lamontagne, Sonia,Metters, Kathleen M.,Sawyer, Nicole,Slipetz, Deborah,Truchon, Jean Francois,Labelle, Marc
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p. 3813 - 3816
(2007/10/03)
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