- Copper-catalyzed domino halide exchange-cyanation of aryl bromides
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An efficient copper-catalyzed domino halogen exchange-cyanation procedure for aryl bromides was developed utilizing 10 mol % CuI, 20 mol % KI, 1.0 equiv of the inexpensive N,N′-dimethylethylenediamine as ligand, and 1.2 equiv of NaCN in toluene at 110 °C. The new method represents a significant improvement over the traditional Rosenmund-von Braun reaction: the reaction conditions are much milder, and the use of stoichiometric amounts of copper(I) cyanide and polar solvents is avoided; therefore the isolation and purification of the aromatic nitrile products is greatly simplified. In addition, the new method exhibits excellent functional group compatibility comparable to that of the analogous Pd-catalyzed cyanation methodology. Copyright
- Zanon, Jacopo,Klapars, Artis,Buchwald, Stephen L.
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- Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
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We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
- Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
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p. 1397 - 1405
(2020/02/04)
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- Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
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Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
- Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
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p. 19257 - 19262
(2019/12/02)
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- Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile: Via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine
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We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me4-DHP). Si-Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.
- Ueda, Yohei,Tsujimoto, Nagataka,Yurino, Taiga,Tsurugi, Hayato,Mashima, Kazushi
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p. 994 - 999
(2019/02/03)
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- N-alkyl-cyanopyrazole synthetic method
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The invention discloses an N-alkyl-cyanopyrazole synthetic method which comprises the following step of by taking 1-alkyl-1H-pyrazole formaldehyde or a derivative thereof, ammonia water, sodium bromate and acetic acid as raw materials and water as a reaction solvent to obtain N-alkyl-cyanopyrazole . The synthetic method provided by the invention is simple in technology without using extremely toxic substances, convenient in synthesis, high in yield, convenient in purification of an obtained product and beneficial to large-scale industrial production.
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Paragraph 0032
(2018/11/22)
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- Mild palladium-catalyzed cyanation of (hetero)aryl halides and triflates in aqueous media
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A mild, efficient, and low-temperature palladium-catalyzed cyanation of (hetero)aryl halides and triflates is reported. Previous palladium-catalyzed cyanations of (hetero)aryl halides have required higher temperatures to achieve good catalytic activity. This current reaction allows the cyanation of a general scope of (hetero)aryl halides and triflates at 2-5 mol % catalyst loadings with temperatures ranging from rt to 40 °C. This mild method was applied to the synthesis of lersivirine, a reverse transcriptase inhibitor.
- Cohen, Daniel T.,Buchwald, Stephen L.
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supporting information
p. 202 - 205
(2015/01/30)
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- New application of heterocyclic diazonium salts. Synthesis of pyrazolo[3,4-d][1,2,3]triazin-4-ones and imidazo[4,5-d][1,2,3]triazin-4-ones
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The pyrazolo[3,4-d][1,2,3]triazin-4-ones 3 and imidazo[4,5-d][1,2,3] triazin-4-ones 4 are analogs structurally related to purines that have showed a wide and significant variety of biological activity. These compounds were synthesized by one-pot diazotization of 5-amino-1H-pyrazole-4-carbonitriles 1 and 5-amino-1H-imidazole-4-carbonitriles 2, respectively.
- Colomer, Juan Pablo,Moyano, Elizabeth Laura
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p. 1561 - 1565
(2011/05/05)
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- New application of heterocyclic diazonium salts: Synthesis of new pyrazolo[3,4-d][1,2,3]triazin-4-ones
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7-Substituted 3,7-dihydro-4H-pyrazolo[3,4-d][1,2,3]triazin-4-ones 2a-d were conveniently prepared by direct diazotization of 5-aminopyrazole-4- carbonitriles 1a-d in HCl media. Different reaction conditions and the effects of substituents on N-1 of the pyrazole ring were studied. A possible mechanistic exlpanation of the observed process is proposed. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Moyano, Elizabeth L.,Colomer, Juan Pablo,Yranzo, Gloria I.
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experimental part
p. 3377 - 3381
(2009/04/06)
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- ARYL SULFONAMIDES
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The present invention relates to compounds that modulate various chemokine receptors. These compounds are useful for treating inflammatory and immune diseases.
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Page/Page column 180
(2010/02/14)
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- COPPER-CATALYZED FORMATION OF CARBON-HETEROATOM AND CARBON-CARBON BONDS
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One aspect of the present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-sulfur bond between the sulfur atom of a thiol moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper(II)-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-carbon bond between the carbon atom of cyanide ion and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In another embodiment, the present invention relates to a copper-catalyzed method of transforming and aryl, heteroaryl, or vinyl iodide. Yet another embodiment of the present invention relates to a tandem method, which may be practiced in a single reaction vessel, wherein the first step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl iodide from the corresponding aryl, heteroaryl, or vinyl chloride or bromide; and the second step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl nitrile, amide or sulfide from the aryl, heteroaryl, or vinyl iodide formed in the first step.
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- PYRAZOLES 3. N-1 PROTECTED 4-SUBSTITUTED PYRAZOLES - SYNTHESIS AND NMR INVESTIGATION
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13C-Nmr Data (chemical shifts, substituent chemical shifts (SCS), coupling constants) are reported for 26 1,4-disubstituted pyrazoles, bearing a benzyl, benzoyl or (substituted) benzenesulfonyl protecting group at N-1.The pyrazole derivatives 8a-d were pr
- Heinisch, Gottfried,Holzer, Wolfgang
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p. 2443 - 2458
(2007/10/02)
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