- Palladium-catalyzed aryl group transfer from triarylphosphines to arylboronic acids
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A study of Pd-catalyzed arylation of arylboronic acids with triarylphosphines is presented. Various parameters of this transformation, such as the oxygen presence, choice of solvent, temperature, palladium source, bases and oxidants, were tested and the optimal conditions of the aryl transfer were determined. The effect of electron-withdrawing and electron-donating substituents on the aryl groups of both reactants was also investigated. The unusual transfer of the acetate group from Pd(OAc)2 to p-nitrophenylboronic acid in the presence of PAr3 is reported. A plausible mechanism of the Pd-catalyzed aryl group transfer from PAr3 to the arylboronic acid is proposed.
- Enright, Dale R.,Gogate, Akash R.,Smoliakova, Irina P.,Vasireddy, Purna C. R.
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- Iridium-Catalyzed Site-Selective Borylation of 8-Arylquinolines
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We report a convenient method for the highly site-selective borylation of 8-arylquinoline. The reaction proceeds smoothly in the presence of a catalytic amount of [Ir(OMe)(cod)] 2and 2-phenylpyridine derived ligand using bis(pinacolato)diborane as the borylating agent. The reactions occur with high selectivity with many functional groups, providing a series of borylated 8-aryl quinolines with good to excellent yield and excellent selectivity. The borylated compounds formed in this method can be transformed into various important synthons by using known transformations.
- Hassan, Mirja Md Mahamudul,Hoque, Md Emdadul,Dey, Sayan,Guria, Saikat,Roy, Brindaban,Chattopadhyay, Buddhadeb
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supporting information
p. 3333 - 3342
(2021/06/18)
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- Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates
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Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.
- Chattopadhyay, Buddhadeb,Hassan, Mirja Md Mahamudul,Hoque, Md Emdadul
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supporting information
p. 5022 - 5037
(2021/05/04)
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- A one-pot protocol for the fluorosulfonation and Suzuki coupling of phenols and bromophenols, streamlined access to biaryls and terphenyls
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A one-pot protocol for the fluorosulfation and Suzuki coupling of phenols is described. The tandem reaction proceeds efficiently at room temperature, and various biaryls and biaryl fluorosulfates were obtained in good to excellent yields. Furthermore, biaryl fluorosulfates were utilized as versatile building blocks for the preparation of terphenyls. The Royal Society of Chemistry 2020.
- Hu, Rui,Li, Xinmin,Ren, Changyue,Yuan, Zeli,Zhang, Hang,Zhang, Tingting
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p. 4748 - 4753
(2020/08/17)
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- Rh(III)-catalyzed C8 arylation of quinoline N-oxides with arylboronic acids
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Herein, we report the first RhIII-catalyzed regioselective C8 arylation of quinoline N-oxides with commercially available arylboronic acids as coupling partners. This procedure is simple, and the reaction shows perfect regioselectivity, a broad substrate scope, and isolated yields of up to 92percent. We demonstrate the utility of the reaction by using it for late-stage functionalization of a fungicide.
- Huang, Yuanqiong,Lv, Xueli,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
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p. 1572 - 1575
(2019/12/24)
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- One-pot Negishi cross-coupling reaction of aryldiazonium salts via Ni catalysis induced by visible-light
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Visible-light induced catalysis is of high interest for its mild and environmentally benign properties. Herein, a general Ni catalysis accelerated by visible-light was successfully developed for one-pot Negishi coupling reactions at room temperature in a short reaction time (2Zn generated in situ from Grignard reagents and ZnBr2. This protocol provides a convenient access to C–C bond formation for important biaryl components. It tolerates various functional groups, and Hammett study illuminates the possiblility of Ni(III)/Ni(I) redox catalytic cycle.
- Wang, Lianjun,Liu, Gao
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- Cobalt-Catalyzed Suzuki Biaryl Coupling of Aryl Halides
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Readily accessed cobalt pre-catalysts with N-heterocyclic carbene ligands catalyze the Suzuki cross-coupling of aryl chlorides and bromides with alkyllithium-activated arylboronic pinacolate esters. Preliminary mechanistic studies indicate that the cobalt
- Asghar, Soneela,Tailor, Sanita B.,Elorriaga, David,Bedford, Robin B.
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p. 16367 - 16370
(2017/12/07)
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- Cobalt-Catalyzed Cross-Coupling Reactions of Arylboronic Esters and Aryl Halides
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An efficient cobalt catalyst system for the Suzuki-Miyaura cross-coupling reaction of arylboronic esters and aryl halides has been identified. In the presence of cobalt(II)/terpyridine catalyst and potassium methoxide, a diverse array of (hetero)biaryls have been prepared in moderate to excellent yields.
- Duong, Hung A.,Wu, Wenqin,Teo, Yu-Yuan
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supporting information
p. 4363 - 4366
(2017/12/05)
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- From Anilines to Quinolines: Iodide- and Silver-Mediated Aerobic Double C?H Oxidative Annulation–Aromatization
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Quinoline synthesis from easily accessible raw materials such as anilines is a valuable and meaningful task. Herein, we communicate an iodide- and silver-mediated C?H/C?H oxidative annulation–aromatization between anilines and allyl alcohols. This protocol provides a direct route to the synthesis of quinoline derivatives from inexpensive commodities. Various kinds of anilines, even heterocyclic anilines, were shown to be workable substrates, generating the corresponding multi-substituted quinolines in good yields.
- Wu, Jiwei,Liao, Zhixiong,Liu, Dong,Chiang, Chien-Wei,Li, Zheng,Zhou, Zhonghao,Yi, Hong,Zhang, Xu,Deng, Zixin,Lei, Aiwen
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supporting information
p. 15874 - 15878
(2017/10/23)
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- Preparation method for biaryl compound
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The invention provides a preparation method for a biaryl compound. The preparation method comprises the step of performing cross coupling reaction on a substrate A and an organic zinc reagent B under a catalytic effect of a catalyst, thereby acquiring the biaryl compound, wherein a chemical structure of the substrate A is shown in the description; the organic zinc reagent B has the chemical structure shown in the description; and the catalyst is one or more of nickel salt, copper salt and cobalt salt. Compared with the other noble metal catalysts, such as, metal palladium catalyst, the catalyst adopting nickel salt, copper salt or cobalt salt is low in cost, so that the reaction cost of the biaryl compound is greatly reduced. Meanwhile, the aryl sulphonate or aryl halide shown as the substrate A has an excellent electrophilic property, is an electrophilic reagent with an excellent property and has the advantages of easiness in preparation, low cost, high activity and high stability. The substrate A and the organic zinc reagent B have cross coupling reaction under the effect of nickel salt, copper salt or cobalt salt so as to generate the biaryl compound and the reaction yield is higher.
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Paragraph 0071-0073
(2017/07/20)
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- Chemoselective Synthesis of Polysubstituted Pyridines from Heteroaryl Fluorosulfates
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A selection of heteroaryl fluorosulfates were readily synthesized using commercial SO2F2 gas. These substrates are highly efficient coupling partners in the Suzuki reaction. Through judicious selection of Pd catalysts the fluorosulfate functionality is differentiated from bromide and chloride; the order of reactivity being: -Br> -OSO2F> -Cl. Exploiting this trend allowed the stepwise chemoselective synthesis of a number of polysubstituted pyridines, including the drug Etoricoxib. A selection of heteroaryl fluorosulfates were readily synthesized using commercial SO2F2 gas. These substrates are highly efficient coupling partners in the Suzuki reaction. Through judicious selection of Pd catalysts the fluorosulfate functionality is differentiated from bromide and chloride; the order of reactivity being: -Br> -OSO2F> -Cl. Exploiting this trend allowed the stepwise chemoselective synthesis of a number of polysubstituted pyridines, including the drug Etoricoxib.
- Zhang, Enxuan,Tang, Jiaze,Li, Suhua,Wu, Peng,Moses, John E.,Sharpless, K. Barry
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p. 5692 - 5697
(2016/04/20)
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- Visible-light-induced regioselective synthesis of polyheteroaromatic compounds
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A method for visible-light-induced synthesis of polyheteroaromatics from 2-heteroaryl-substituted anilines and heteroarylalkynes was developed. The process, which uses fac-Ir(ppy)3 as the photocatalyst and tBuONO as the diazotization reagent, is highly regioselective.
- Chatterjee, Tanmay,Choi, Myung Gil,Kim, Jun,Chang, Suk-Kyu,Cho, Eun Jin
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p. 4203 - 4206
(2016/03/19)
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- General copper-catalyzed coupling of alkyl-, aryl-, and alkynylaluminum reagents with organohalides
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We report the first example of a very general Cu-catalyzed cross-coupling of organoaluminum reagents with organohalides. The reactions proceed for the couplings of alkyl-, aryl-, and alkynylaluminum reagents with aryl and heteroaryl halides and vinyl bromides, affording the cross-coupled products in good to excellent yields. Both primary and secondary alkylaluminum reagents can be utilized as organometallic coupling partners. These reactions are not complicated by β-hydride elimination, and as a result rearranged products are not observed with secondary alkylaluminum reagents even for couplings with heteroaryl halides under "ligand-free" conditions. Radical clock experiment with a radical probe and relative reactivity study of Ph3Al with two haloarenes, 1-bromonaphthalene and 4-chlorobenzonitrile, having two different redox potentials indicates that the reaction does not involve free aryl radicals and radical anions as intermediates. These results combined with the result of the Hammett plot obtained by reacting Ph3Al with iodoarenes containing p-H, p-Me, p-F, and p-CF3 substituents, which shows a linear curve (R2 = 0.99) with a ρ value of +1.06, suggest that the current transformation follows an oxidative addition-reductive elimination pathway.
- Shrestha, Bijay,Thapa, Surendra,Gurung, Santosh K.,Pike, Ryan A. S.,Giri, Ramesh
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p. 787 - 802
(2016/02/18)
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- Carbon-carbon cross-coupling reactions catalyzed by a two-coordinate nickel(II)-Bis(amido) complex via observable NiI, NiII, and NiIII intermediates
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Recently, the development of more sustainable catalytic systems based on abundant first-row metals, especially nickel, for cross-coupling reactions has attracted significant interest. One of the key intermediates invoked in these reactions is a NiIII-alkyl species, but no such species that is part of a competent catalytic cycle has yet been isolated. Herein, we report a carbon-carbon cross-coupling system based on a two-coordinate Ni II-bis(amido) complex in which a NiIII-alkyl species can be isolated and fully characterized. This study details compelling experimental evidence of the role played by this NiIII-alkyl species as well as those of other key NiI and NiII intermediates. The catalytic cycle described herein is also one of the first examples of a two-coordinate complex that competently catalyzes an organic transformation, potentially leading to a new class of catalysts based on the unique ability of first-row transition metals to accommodate two-coordinate complexes.
- Lipschutz, Michael I.,Tilley, T. Don
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supporting information
p. 7290 - 7294
(2014/07/21)
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- A nickel precatalyst for efficient cross-coupling reactions of aryl tosylates with arylboronic acids: Vital role of dppf
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An air-stable and easy-to-handle nickel precatalyst, (9-phenanthrenyl) Ni(II)(PPh3)2Cl, was examined for the cross-coupling reactions of aryl tosylates with arylboronic acids. Under the optimized reaction conditions, the catalytic system tolerates a wide range of activated, neutral and deactivated substrates. The selectivity of this cross-coupling reaction towards aryl tosylates and arylboronic acids has been investigated. It is proposed that ligand 1,1′-bis(diphenylphosphino)ferrocene (dppf) plays a key role in the coupling by enforcing a cis geometry in key intermediates and the active Ni(0) species.
- Hu, Feng,Lei, Xiangyang
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p. 3854 - 3858
(2014/06/09)
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- Copolymer-incarcerated nickel nanoparticles with N-heterocyclic carbene precursors as active cross-linking agents for Corriu-Kumada-Tamao reaction
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We have developed heterogeneous polymer-incarcerated nickel nanoparticles (NPs), which catalyze cross-coupling reactions. The matrix structure of these catalysts incorporates both N-heterocyclic carbenes (NHCs) as ligands and Ni-NPs, thanks to a new design of cross-linking agents in polymer supports. These embedded NHCs were detected by field gradient swollen-resin magic angle spinning NMR analysis. They were successfully applied to Corriu-Kumada-Tamao reactions with a broad substrate scope including functional group tolerance, and the catalyst could be recovered and reused several times without loss of activity.
- Soule, Jean-Francois,Miyamura, Hiroyuki,Kobayashi, Shu
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supporting information
p. 10602 - 10605
(2013/08/23)
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- Synthesis of 8-arylquinolines via one-pot Pd-catalyzed borylation of quinoline-8-yl halides and subsequent Suzuki-Miyaura coupling
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A one-pot process has been developed for the synthesis of 8-arylquinolines via Pd-catalyzed borylation of quinoline-8-yl halides and subsequent Suzuki-Miyaura coupling with aryl halides using n-BuPAd2 as ligand. Yields of up to 98% were obtaine
- Zhang, Yongda,Gao, Joe,Li, Wenjie,Lee, Heewon,Lu, Bruce Z.,Senanayake, Chris H.
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supporting information; experimental part
p. 6394 - 6400
(2011/10/01)
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- Rh(NHC)-catalyzed direct and selective arylation of quinolines at the 8-position
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A new catalytic protocol for the regioselective direct arylation of quinoline derivatives at the 8-position has been developed. The reaction is catalyzed by a Rh(NHC) system, and the choice of the NHC ligand was most important for achieving high reactivit
- Kwak, Jaesung,Kim, Min,Chang, Sukbok
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supporting information; experimental part
p. 3780 - 3783
(2011/05/05)
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- Palladium-catalyzed Suzuki-Miyaura reactions of potassium aryl- and heteroaryltrifluoroborates with aryl- and heteroaryl triflates
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The Suzuki-Miyaura cross-coupling of potassium aryl-and heteroaryltrifluoroborates with aryl- and heteroaryl triflates is reported. The catalyst system provides good to excellent yields using sterically hindered and electronically diverse coupling partners. Georg Thieme Verlag Stuttgart.
- Molander, Gary A.,Petrillo, Daniel E.,Landzberg, Nicole R.,Rohanna, John C.,Biolatto, Betina
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p. 1763 - 1766
(2007/10/03)
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- Palladium Cross-Coupling Reactions of Aryl Fluorosulfonates: An Alternative to Triflate Chemistry
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A new and efficient electrophilic partner for palladium(0)-catalyzed cross coupling is reported.Aryl fluorosulfonates are readily prepared in high yield by treatment of the appropriate phenol with fluorosulfonate anhydride.The palladium-catalyzed coupling reactions of these fluorosulfonates with vinyl- and aryltin reagents, as well as organozinc chlorides, takes place under mild conditions in a regio- and stereoselective manner.
- Roth, Gregory P.,Fuller, Carl E.
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p. 3493 - 3496
(2007/10/02)
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- Selectivity in the Hydrogenation of 6- and 8-Substituted-quinolines
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Quinoline (1) and the 6- or 8-substituted-quinolines (2)-(14) (R = Me, Pri, But, Ph, OMe, OH, CF3, or F) were hydrogenated catalytically on platinum under either weakly basic (solvent MeOH) or strongly acidic (solvent CF3CO2H) conditions.In methanol the only product was the corresponding 1,2,3,4-tetrahydro-compound.In trifluoroacetic acid, compounds hydrogenated in the benzene ring were isolated as major products; both electron-withdrawing and electron-donating substituents at C-6 or C-8 cause (sometimes drastic) reduction in yield.The products were characterized by their 1H and 13C n.m.r. spectra.
- Hoenel, Michael,Vierhapper, Friedrich W.
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p. 1933 - 1939
(2007/10/02)
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