- AIR-STABLE NI(0)-OLEFIN COMPLEXES AND THEIR USE AS CATALYSTS OR PRECATALYSTS
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The present invention relates to air stable, binary Ni(0)-olefin complexes and their use in organic synthesis.
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Page/Page column 17-19
(2021/02/05)
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- Ni(COD)(DQ): An Air-Stable 18-Electron Nickel(0)–Olefin Precatalyst
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We report that Ni(COD)(DQ) (COD=1,5-cyclooctadiene, DQ=duroquinone), an air-stable 18-electron complex originally described by Schrauzer in 1962, is a competent precatalyst for a variety of nickel-catalyzed synthetic methods from the literature. Due to its apparent stability, use of Ni(COD)(DQ) as a precatalyst allows reactions to be conveniently performed without use of an inert-atmosphere glovebox, as demonstrated across several case studies.
- Apolinar, Omar,Derosa, Joseph,Eastgate, Martin D.,Engle, Keary M.,Joannou, Matthew V.,Li, Zi-Qi,Tran, Van T.,Wisniewski, Steven R.
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supporting information
p. 7409 - 7413
(2020/04/10)
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- An N-Heterocyclic Carbene-Nickel Half-Sandwich Complex as a Precatalyst for Suzuki-Miyaura Coupling of Aryl/Heteroaryl Halides with Aryl/Heteroarylboronic Acids
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A nickel half-sandwich complex supported by our original NHC ligand was developed as a robust precatalyst for Suzuki-Miyaura cross-coupling. The addition of PPh3 was a crucial element in the suppression of side reactions and in accelerating the cross-coupling reaction. By employing the optimal conditions, aryl-aryl, heteroaryl-aryl, and heteroaryl-heteroaryl couplings were achieved.
- Ando, Shin,Matsunaga, Hirofumi,Ishizuka, Tadao
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p. 1266 - 1272
(2018/06/18)
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- A new route towards dithienoquinazoline and benzo[f]thieno[3,2-h]quinazoline systems using Pd-catalyzed intramolecular cyclization under microwave irradiation
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A novel synthetic route to novel thienoacene systems bearing a fused pyrimidine ring is proposed. The commercially available 5-bromopyrimidine is used as the starting material to obtain various dithienoquinazoline and benzo[f]thieno[3,2-h]quinazoline syst
- Verbitskiy, Egor V.,Rusinov, Gennady L.,Chupakhin, Oleg N.,Charushin, Valery N.
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p. 204 - 216
(2016/07/06)
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- Sustainable Fe-ppm Pd nanoparticle catalysis of Suzuki-Miyaura cross-couplings in water
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Most of today's use of transition metal-catalyzed cross-coupling chemistry relies on expensive quantities of palladium (Pd). Here we report that nanoparticles formed from inexpensive FeCl3 that naturally contains parts-per-million (ppm) levels of Pd can catalyze Suzuki-Miyaura reactions, including cases that involve highly challenging reaction partners. Nanomicelles are employed to both solubilize and deliver the reaction partners to the Fe-ppm Pd catalyst, resulting in carbon-carbon bond formation. The newly formed catalyst can be isolated and stored at ambient temperatures. Aqueous reaction mixtures containing both the surfactant and the catalyst can be recycled.
- Handa, Sachin,Wang, Ye,Gallou, Fabrice,Lipshutz, Bruce H.
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p. 1087 - 1091
(2015/09/21)
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- Synthesis, and structure-activity relationship for C(4) and/or C(5) thienyl substituted pyrimidines, as a new family of antimycobacterial compounds
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Abstract Combination of the Suzuki cross-coupling and nucleophilic aromatic substitution of hydrogen (SNH) reactions proved to be a convenient method for the synthesis of C(4) and/or C(5) mono(thienyl) and di(thienyl) substituted pyrimidines from commerci
- Verbitskiy, Egor V.,Cheprakova, Ekaterina M.,Slepukhin, Pavel A.,Kravchenko, Marionella A.,Skornyakov, Sergey N.,Rusinov, Gennady L.,Chupakhin, Oleg N.,Charushin, Valery N.
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p. 225 - 234
(2015/05/27)
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- Synthesis of heteroaryl compounds through cross-coupling reaction of aryl bromides or benzyl halides with thienyl and pyridyl aluminum reagents
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An efficient method for synthesis of useful biaryl building blocks containing 2-thienyl, 3-thienyl, 2-pyridyl, and 3-pyridyl moieties was provided through cross-coupling reactions of aryl bromides or benzyl halides with heteroaryl aluminum reagents in the presence of Pd(OAc)2 and (o-tolyl)3P. The coupling reaction also worked efficiently with heteroaryl bromides affording series of heterobiaryl compounds. The reaction of phenylbromide with in situ prepared 3-pyridyl aluminum was demonstrated to afford the product 8a in high yield. Additionally, the catalytic system was also suited well for the coupling reaction of benzyl halides with pyridyl aluminum reagents to afford series of pyridyl-arylmethane.
- Chen, Xu,Zhou, Lingmin,Li, Yimei,Xie, Tao,Zhou, Shuangliu
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p. 230 - 239
(2014/01/17)
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- A highly efficient memantine-modified palladium catalyst for Suzuki-Miyaura cross-coupling reaction
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A new simple Pd(memantine)2Cl2 complex was synthesized and characterized by 1H NMR, 13C NMR and X-ray single crystal structure determination. The Suzuki-Miyaura reaction of aryl bromides catalyzed by Pd(memantine)2Cl2 complex was investigated in air with different temperature. The high turnover numbers of 650,000 have been obtained in the reaction of 4-bromonitrobenzene with phenylboronic acid at 80 °C. At room temperature, the complex also showed high activity for Suzuki-Miyaura cross-coupling reaction of aryl bromides with a wide range of functional groups under air, and the turnover number of up to 99,000 was achieved. The catalytic system also gives good yields toward the reaction of several heteroaryl bromides with thiophenylboronic acid.
- Wu, Qinxu,Wu, Leilei,Zhang, Lei,Fu, Haiyan,Zheng, Xueli,Chen, Hua,Li, Ruixiang
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p. 3471 - 3477
(2014/05/06)
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- Tetraphosphine/palladium-catalyzed Suzuki-Miyaura coupling of heteroaryl halides with 3-pyridine- and 3-thiopheneboronic acid: An efficient catalyst for the formation of biheteroaryls
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An easily prepared tetraphosphine N,N,N′,N′- tetra(diphenylphosphinomethyl)-1,2-ethylenediamine (L1) associated with [Pd(η3-C3H5)Cl]2 affords an efficient catalyst for Suzuki-Miyaura coupling of 3-pyridineboronic acid with heteroaryl bromides. Reaction could be performed with as little as 0.02 mol% catalyst and a high turnover number of 2500 is obtained. A wide range of substrates is investigated with satisfactory yields, and good compatibility with aminogroup-substituted pyridines and unprotected indole is exhibited. This protocol can also be applied successfully to the reaction of heteroaryl bromides with 3-thiopheneboronic acid. This Pd-tetraphosphine catalyst efficiently restrains the poisoning effect from heteroaryls, and shows good stability and longevity. Copyright 2013 John Wiley & Sons, Ltd. An easily prepared tetraphosphine L1 was successfully used in Pd catalyzed Suzuki reaction of heteroaryl bromides with 3-pyridineboronic acid. A high turnover number of 2 500 was achieved and a wide range of heteroaryl halides including aminopyridines and indole was tolerated. With this protocol the coupling of 3-thiopheneboronic acid with heteroaryl bromides could also proceed in good yields. This catalyst system efficiently restrained poisoning effect from heteroaryls, and exhibited good stability and longevity. Copyright
- Wang, Kun,Fu, Qi,Zhou, Rong,Zheng, Xueli,Fu, Haiyan,Chen, Hua,Li, Ruixiang
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p. 232 - 238
(2013/05/08)
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- Nickel-catalyzed Suzuki-Miyaura couplings in green solvents
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The nickel-catalyzed Suzuki-Miyaura coupling of aryl halides and phenol-derived substrates with aryl boronic acids using green solvents, such as 2-Me-THF and tert-amyl alcohol, is reported. This methodology employs the commercially available and air-stable precatalyst, NiCl2(PCy 3)2, and gives biaryl products in synthetically useful to excellent yields. Using this protocol, bis(heterocyclic) frameworks can be assembled efficiently.
- Ramgren, Stephen D.,Hie, Liana,Ye, Yuxuan,Garg, Neil K.
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supporting information
p. 3950 - 3953
(2013/09/02)
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- A general method for Suzuki-Miyaura coupling reactions using lithium triisopropyl borates
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Conditions for the Suzuki-Miyaura coupling of lithium triisopropyl borates are reported, as well as a procedure for a one-pot lithiation, borylation, and subsequent Suzuki-Miyaura coupling of various heterocycles with aryl halides. These borate species are much more stable toward protodeboronation than the corresponding boronic acids and can conveniently be stored on benchtop at room temperature.
- Oberli, Matthias A.,Buchwald, Stephen L.
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supporting information
p. 4606 - 4609
(2012/10/30)
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- Highly reactive, single-component nickel catalyst precursor for Suzuki-Miyuara cross-coupling of heteroaryl boronic acids with heteroaryl halides
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One for all: The coupling of a range of nitrogen- and sulfur-containing heteroaryl halides with five-membered nitrogen-, oxygen-, and sulfur-containing heteroaryl boronic acids were achieved in high yields with only 0.5 mol % of the single-component nickel precatalyst [(dppf)NiCl(cinnamyl)] (dppf=1,1′- bis(diphenylphosphanyl)ferrocene). The reaction demonstrates good functional group compatibility, and is easily conducted on a large scale without a dry box. Copyright
- Ge, Shaozhong,Hartwig, John F.
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supporting information
p. 12837 - 12841
(2013/02/22)
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- Consecutive SNH and Suzuki-Miyaura cross-coupling reactions-an efficient synthetic strategy to pyrimidines bearing pyrrole and indole fragments
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The combination of the Suzuki-Miyaura cross-coupling and nucleophilic aromatic substitution of hydrogen reactions is a versatile tool for the syntheses of 4-(1R-pyrrol-2-yl)-and 4-(1R-indol-3-yl)-5-(hetero)aryl-substituted pyrimidines from commercially available 5-bromopyrimidine. The S NH [AE, (addition-elimination)] and SN H [AO, (addition-oxidation)] reactions of 5-bromopyrimidine with pyrroles and indoles were studied by gas chromatography-mass spectrometry. The structures of the intermediate σH adducts as well as the pyrrole-(hetero)arylpyrimidine and indole-(hetero)arylpyrimidine dyads were established for the first time by X-ray crystal structure analysis.
- Verbitskiy, Egor V.,Rusinov, Gennady L.,Charushin, Valery N.,Chupakhin, Oleg N.,Cheprakova, Ekaterina M.,Slepukhin, Pavel A.,Pervova, Marina G.,Ezhikova, Marina A.,Kodess, Mikhail I.
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supporting information
p. 6612 - 6621
(2013/01/15)
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- Micellar catalysis of Suzuki-Miyaura cross-couplings with heteroaromatics in water
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(Chemical Equation Presented) Pd-catalyzed couplings involving several heteroaromatic halides (bromides and chlorides) as well as boronic acids can be done under exceedingly mild conditions (between rt and 40 °C) in pure water using commercially available Pd catalysts and PTS, a nanomicelle-forming amphiphile.
- Lipshutz, Bruce H.,Abela, Alexander R.
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supporting information; experimental part
p. 5329 - 5332
(2009/06/06)
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- Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of potassium aryl- and heteroaryltrifluoroborates
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An extended study of the reactivity of potassium aryl- and heteroaryltrifluoroborates in Suzuki-Miyaura cross-coupling reactions is presented. The coupling of aryl- and electron-rich heteroaryltrifluoroborates with aryl and activated heteroaryl bromides proceeds readily under ligandless conditions. When deactivated aryl- and heteroaryltrifluoroborates are coupled with aryl and heteroaryl bromides and chlorides, a low loading (0.5-2%) of PdCl2(dppf)·CH2Cl2 efficiently catalyzes the reactions. Under either condition, reactions can generally be carried out in an open atmosphere.
- Molander, Gary A.,Biolatto, Betina
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p. 4302 - 4314
(2007/10/03)
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- Nickel-catalyzed suzuki-miyaura coupling in t-amyl alcohol for the preparation of 5-(Furan-3-yl)pyrimidine
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Transition metal-catalyzed cross-couplings are versatile methods for carbon-carbon and carbon-heteroatom bond formation. Traditionally, palladium catalysts have been most commonly utilized for this type of transformation; however, there has been a significant interest in the development of cross-coupling reactions that rely on non-precious metal catalysts. In particular, nickel has emerged as an alternative to palladium due to several factors. The article reports nickel-catalyzed Suzuki-Miyaura coupling in t-amyl alcohol for the preparation of 5-(Furan-3-yl)pyrimidine.
- Hie, Liana,Garg, Neil K.
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