- Heteroarylation method of amine
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The invention discloses a heteroarylation method of amine, and the method comprises the following steps of: mixing an amine compound, heteroaromatic hydrocarbon, a photocatalyst and an organic solventto obtain a solution A; and in an inert gas atmosphere, irradiating the solution A with visible light, and carrying out reaction to obtain a heteroarylated product of amine. According to the method,under mild conditions, free radical coupling of amine compounds and heteroaromatic compounds is efficiently achieved through visible light irradiation, and various heteroarylamines are synthesized. The method has good functional group compatibility and high regioselectivity, can be further applied to later modification of bioactive molecules, and shows a good industrial application prospect.
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Paragraph 0060-0070; 0076
(2021/02/24)
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- Method for synthesizing 1-aminoisoquinoline skeleton by rhodium-catalyzed 4-phenyl oxadiazolone and vinylene carbonate
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The invention discloses a method for generating 1-aminoisoquinoline and a derivative thereof through a rhodium-catalyzed reaction of a 4-phenyl oxadiazolone compound and vinylene carbonate. According to the invention, a 4-phenyl oxadiazolone compound is used as a raw material and reacts with vinylene carbonate under the catalysis of transition metal rhodium to generate an isoquinoline ring. The synthesis operation steps are simple, the atom economy is high, the application range of the substrate is wide, the post-treatment operation is simpler, the implementation feasibility is high, and a foundation is laid for industrial production and wide application of the aminoisoquinoline compound.
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Paragraph 0010-0011
(2021/12/07)
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- Catalyst-free synthesis of substituted pyridin-2-yl, quinolin-2-yl, and isoquinolin-1-yl carbamates from the corresponding hetaryl ureas and alcohols
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A novel catalyst-free synthesis ofN-pyridin-2-yl,N-quinolin-2-yl, andN-isoquinolin-1-yl carbamates utilizes easily accessibleN-hetaryl ureas and alcohols. The proposed environmentally friendly technique is suitable for the good-to-high yielding synthesis of a wide range ofN-pyridin-2-yl orN-quinolin-2-yl substituted carbamates featuring electron-donating and electron-withdrawing groups in the azine rings and containing various primary, secondary, and even tertiary alkyl substituents at the oxygen atom (48-94%; 31 examples). The DFT calculation and experimental study showed that the reaction proceeds through the intermediate formation of hetaryl isocyanates. The method can be applied to obtainN-isoquinolin-1-yl carbamates, although in lower yields, and ethyl benzo[h]quinolin-2-yl carbamate has also been successfully synthesized (68%).
- Baykov, Sergey V.,Boyarskaya, Irina A.,Boyarskiy, Vadim P.,Geyl, Kirill K.,Kasatkina, Svetlana O.
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p. 6059 - 6065
(2021/07/21)
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- Rhodium(III)-Catalyzed Oxidative Annulation of Amidines with Alkynes via Sequential C?H Bond Activation
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In this paper, a rhodium-catalyzed sequential two-fold ortho-C?H functionalization of N-phenylbenzimidamide with internal alkyne is reported. The double C?H activations proved viable in a one-pot fashion with the assistance of C=N and C?N bonds, providing a series of benzimidazoisoquinolines with high levels of positional selectivity control. The operationally simple transformation showed high functional group compatibility and featured the cleavage of C?H bonds located on different a moiety of the N-phenylbenzimidamide substrates. Detailed mechanistic studies provided strong support for C?H bond cleavage on the N-phenyl ring to be preferential compared with C?H bond cleavage on C-phenyl ring. As a multifunctional catalytic platform, the rhodium catalyst conducted two independent and compatible catalytic cycles in one pot.
- Meng, Yan-Yu,Zhu, Wen-Jing,Song, Yuan-Yuan,Bu, Gang-Gang,Zhang, Li-Juan,Xu, Fen
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supporting information
p. 1290 - 1294
(2021/02/01)
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- Metal-free, redox-neutral, site-selective access to heteroarylamine via direct radical?radical cross-coupling powered by visible light photocatalysis
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Transition-metal-catalyzed C?N bond-forming reactions have emerged as fundamental and powerful tools to construct arylamines, a common structure found in drug agents, natural products, and fine chemicals. Reported herein is an alternative access to heteroarylamine via radical?radical cross-coupling pathway, powered by visible light catalysis without any aid of external oxidant and reductant. Only by visible light irradiation of a photocatalyst, such as a metal-free photocatalyst, does the cascade single-electron transfer event for amines and heteroaryl nitriles occur, demonstrated by steady-state and transient spectroscopic studies, resulting in an amine radical cation and aryl radical anion in situ for C?N bond formation. The metal-free and redox economic nature, high efficiency, and site-selectivity of C?N cross-coupling of a range of available amines, hydroxylamines, and hydrazines with heteroaryl nitriles make this protocol promising in both academic and industrial settings.
- Zhou, Chao,Lei, Tao,Wei, Xiang-Zhu,Ye, Chen,Liu, Zan,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
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p. 16805 - 16813
(2020/11/09)
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- Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration
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Deprotonative directed ortho cupration of aromatic/heteroaromatic C-H bond and subsequent oxidation with t-BuOOH furnished functionalized phenols in high yields with high regio- and chemoselectivity. DFT calculations revealed that this hydroxylation reaction proceeds via a copper (I → III → I) redox mechanism. Application of this reaction to aromatic C-H amination using BnONH2 efficiently afforded the corresponding primary anilines. These reactions show broad scope and good functional group compatibility. Catalytic versions of these transformations are also demonstrated.
- Tezuka, Noriyuki,Shimojo, Kohei,Hirano, Keiichi,Komagawa, Shinsuke,Yoshida, Kengo,Wang, Chao,Miyamoto, Kazunori,Saito, Tatsuo,Takita, Ryo,Uchiyama, Masanobu
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supporting information
p. 9166 - 9171
(2016/08/05)
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- Ligandless copper-catalyzed coupling of heteroaryl bromides with gaseous ammonia
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A range of different N- and S-containing heterocyclic bromides can be efficiently coupled with gaseous ammonia in the presence of copper(II) acetylacetonate [Cu(acac)2] as catalyst and in the absence of additional ligands. Unstable aminothiophenes and aminobenzothiophenes can be further reacted in situ to afford functionalized derivatives. Copyright
- Fantasia, Serena,Windisch, Johannes,Scalone, Michelangelo
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supporting information
p. 627 - 631
(2013/04/11)
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- Mild and highly selective palladium-catalyzed monoarylation of ammonia enabled by the use of bulky biarylphosphine ligands and palladacycle precatalysts
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A method for the Pd-catalyzed arylation of ammonia with a wide range of aryl and heteroaryl halides, including challenging five-membered heterocyclic substrates, is described. Excellent selectivity for monoarylation of ammonia to primary arylamines was achieved under mild conditions or at rt by the use of bulky biarylphosphine ligands (L6, L7, and L4) as well as their corresponding aminobiphenyl palladacycle precatalysts (3a, 3b, and 3c). As this process requires neither the use of a glovebox nor high pressures of ammonia, it should be widely applicable.
- Cheung, Chi Wai,Surry, David S.,Buchwald, Stephen L.
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supporting information
p. 3734 - 3737
(2013/08/23)
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- NOVEL CATALYSTS
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The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.
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Page/Page column 66
(2012/06/01)
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- A highly versatile catalyst system for the cross-coupling of aryl chlorides and Amines
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The syntheses of 2-(di-tertbutylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamantylphosphino)-N,N-dimethylaniline (L2, 74%), and their application in BuchwaldHartwig amination, are reported. In combination with [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2, these structurally simple and air-stable P,N ligands enable the cross-coupling of aryl and heteroaryl chlorides, including those bearing as substituents enolizable ketones, ethers, esters, carboxylic acids, phenols, alcohols, olefins, amides, and halogens, to a diverse range of amine and related substrates that includes primary alkyl- and arylamines, cyclic and acyclic secondary amines, N-H imines, hydrazones, lithium amide, and ammonia. In many cases, the reactions can be performed at low catalyst loadings (0.5-0.02 mol % Pd) with excellent functional group tolerance and chemoselectivity. Examples of cross-coupling reactions involving 1,4-bromochlorobenzene and iodobenzene are also reported. Under similar conditions, inferior catalytic performance was achieved when using Pd(OAc)2, PdCl2, [PdCl2(cod)] (cod = 1,5-cyclooctadiene), [PdCl 2(MeCN)2], or [Pd2(dba)3] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2 with variants of L1 and L2 bearing less basic or less sterically demanding substituents on phosphorus or lacking an ortto-dimethylamino fragment. Given current limitations associated with established ligand classes with regard to maintaining high activity across the diverse possible range of C-N coupling applications, L1 and L2 represent unusually versatile ligand systems for the cross-coupling of aryl chlorides and amines
- Lundgren, Rylan J.,Sappong-Kumankumah, Antonia,Stradiotto, Mark
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experimental part
p. 1983 - 1991
(2010/07/03)
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- A general and efficient 2-amination of pyridines and quinolines
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(Chemical Equation Presented) Pyridine N-oxides were converted to 2-aminopyridines in a one-pot fashion using Ts2O-t-BuNH2 followed by in situ deprotection with TFA. The amination proceeded in high yields, excellent 2-/4-selectivity, and with good functional group compatibility. 2-Amino (iso)quinolines were also obtained in the same manner. Combined with the simple oxidation of pyridines to pyridine N-oxides, this method provides a general and efficient way for amination of 2-unsubstituted pyridines.
- Yin, Jingjun,Xiang, Bangping,Huffman, Mark A.,Raab, Conrad E.,Davies, Ian W.
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p. 4554 - 4557
(2008/02/04)
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- CFTR channel modulators
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The invention concerns pharmaceutical formulas designed for the treatment of diseases related to CFTR channel dysfunction, such as cystic fibrosis, asthma or diarrhoea. These formulas contain a molecule, coming in the form of a zwitterion at physiological pH, with the formula: where XN or P; YO or S; R1 to R7 represent: -, H, or carbon chains, substituted or not, which may contain heteroatoms; except for betaine.
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Page/Page column 17
(2008/06/13)
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- Isoquinolinamine and phthalazinamine derivatives: corticotropin-releasing factor receptor CRF1 specific ligands
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Disclosed are compounds that are highly selective partial agonists or antagonists at human CRF1 receptors that are useful in the diagnosis and treatment of treating stress related disorders such as post traumatic stress disorder (PTSD) as well as depression, headache and anxiety. The compounds have the formula or the pharmaceutically acceptable salts thereof wherein Ar, R1, R2, R3, R4 and W are various organic and inorganic substituents.
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- 151. Azidinium-Salze. 24. Mitteilung. Thermolyse heterocyclischer Azidinium-tetrafluoroborate
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The thermolysis of some azidinium salts was investigated.It led to a large variety of products which were isolated or identified by GC/MS.Reaction mechanisms are discussed to explain the product formation.
- Huys-Francotte, Martine,Balli, Heinz
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p. 1679 - 1684
(2007/10/02)
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- Regioselectivity of the Amination of Some Nitroisoquinolines by Liquid Ammonia/Potassium Permanganate
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5- and 8-Nitroisoquinoline and some of their derivatives are aminated in a liquid ammonia solution of potassium permanganate to yield the corresponding 6- and 7-amino compounds.From 5,7-dinitroisoquinoline the 6,8-diamino derivative is obtained; 1-nitroisoquinoline has been found to be unreactive.FMO calculations made for a few nitroisoquinolines confirm the experimentally observed regioselectivity of the amination.
- Wozniak, Marian,Baranski, Andrzej,Nowak, Krystyna,Poradowska, Henryka
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p. 653 - 657
(2007/10/02)
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- 192. Azidinium-Salze 23.Mitteilung Photolyse heterocyclischer Azidinium-Salze
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The photochemistry of some azidinium salts was investigated.Their photolysis led to a large variety of products whichh were isolated and identified.Reaction mechanisms involving singlet and triplet nitrene intermediates are discussed to explain the product formation.
- Balli, Heinz,Huys-Francotte, Martine,Schmidlin, Fred
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p. 2045 - 2057
(2007/10/02)
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- Dipyrido [4,3-b] [3,4-f] indoles and process for obtaining them
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The invention relates to compounds of formula: STR1 wherein R'1 =H, OH or an alkyl group, preferably a lower alkyl group, alkylthio or alkoxy, an halogen or an amino group, R'2 =H or a lower alkyl group. These compounds have antitumoral and antiviral properties useful for the treatment of cancers.
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- ELECTRON DEFICIENT HETEROAROMATIC AMMONIOAMIDATES, XVIII. THE SYNTHESIS AND PHOTOCHEMISTRY OF SOME N-ISOQUINOLINO(THIOAMIDATES)
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Thioacylation of isoquinolinioamide furnished the N-isoquinolinio(thioamidates) 2a-2c.Depending on the solvent, 2c exists either as a mixture with its tricyclic tautomer 5, or exclusively as the latter.The NMR and mass spectra, and the photochemistry of compounds 2a-2c are discussed.The photoproducts obtained include 3,4-dimethoxybenzonitrile, 3,4-dimethoxy(thiobenzamide), O-ethyl thiocarbamate, 1(2H)-isoquinolinethione (7a), 1(2H)-isoquinolinone (7b) and thiadiazoloisoquinolin-4-ium-2-olate (8a).Differences between the fragmentation upon electron impact and the photochemistry of the thioamidates of Types 1 and 2, as well as between the photochemistry of the thioamidates 2 and their amidate counterparts of Type 3 are discussed.Potassium permanganate oxidation of thiadiazoloisoquinolin-4-ium-2-thiolate (8b) furnishes the olate 8a and 1-isoquinolyl thiocyanate (12).
- Lempert-Sreter, M.,Lempert, K.,Tamas, J.,Vekey, K.
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p. 259 - 270
(2007/10/02)
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