- Synthesis ofN-aryl amines enabled by photocatalytic dehydrogenation
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Catalytic dehydrogenation (CD)viavisible-light photoredox catalysis provides an efficient route for the synthesis of aromatic compounds. However, access toN-aryl amines, which are widely utilized synthetic moieties,viavisible-light-induced CD remains a significant challenge, because of the difficulty in controlling the reactivity of amines under photocatalytic conditions. Here, the visible-light-induced photocatalytic synthesis ofN-aryl amines was achieved by the CD of allylic amines. The unusual strategy using C6F5I as an hydrogen-atom acceptor enables the mild and controlled CD of amines bearing various functional groups and activated C-H bonds, suppressing side-reaction of the reactiveN-aryl amine products. Thorough mechanistic studies suggest the involvement of single-electron and hydrogen-atom transfers in a well-defined order to provide a synergistic effect in the control of the reactivity. Notably, the back-electron transfer process prevents the desired product from further reacting under oxidative conditions.
- Kim, Jungwon,Kim, Siin,Choi, Geunho,Lee, Geun Seok,Kim, Donghyeok,Choi, Jungkweon,Ihee, Hyotcherl,Hong, Soon Hyeok
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p. 1915 - 1923
(2021/02/22)
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- Mixed er-NHC/phosphine Pd(ii) complexes and their catalytic activity in the Buchwald-Hartwig reaction under solvent-free conditions
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A series of novel (NHC)PdCl2-PR3 complexes were synthesized and fully characterized by 1H, 13C, 31P NMR and FT-IR spectroscopy. These complexes showed high catalytic activity toward solvent-free Buchwald-Hartwig amination. Both primary and secondary amines were efficiently utilized under the same reaction conditions. The solvent-free synthesis of valuable N-aryl carbazoles and similar N-heterocyclic systems was described.
- Ageshina, Alexandra A.,Sterligov, Grigorii K.,Rzhevskiy, Sergey A.,Topchiy, Maxim A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Nechaev, Mikhail S.,Asachenko, Andrey F.,Bermeshev, Maxim V.,Melnikova, Elizaveta K.
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supporting information
p. 3447 - 3452
(2019/04/30)
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- Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates
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A simple and efficient method for transition-metal-free N-arylation of various amines by triarylsulfonium triflates is described. Both aliphatic and aromatic amines were smoothly converted at 80 °C in the presence of tBuOK or KOH to give the corresponding mono N-arylated products in good to high yields. The molar ratios of the reactants and the choice of bases had a big effect on the reaction. When a large excess of [Ph3S][OTf] and tBuOK were employed for primary amines under the standard conditions, the bis(N-phenyl) products were predominantly formed. This method was also applicable to the synthesis of bioactive N-phenyl amino acid derivatives. The control experiments, the deuterium labelling study, and the presence of regioisomers of N-arylated products when using 4-substituted triarylsulfonium triflates suggested that the reaction might proceed through an aryne intermediate. The present protocol demonstrated that triarylsulfonium salts are versatile arylation reagents in the construction of CAr?N bonds.
- Tian, Ze-Yu,Ming, Xiao-Xia,Teng, Han-Bing,Hu, Yu-Tian,Zhang, Cheng-Pan
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supporting information
p. 13744 - 13748
(2018/09/14)
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- Synergistic Ligand Effect between N-Heterocyclic Carbene (NHC) and Bicyclic Phosphoramidite (Briphos) Ligands in Pd-Catalyzed Amination
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A synergistic ligand effect between NHC and phosphorus ligands in Pd-catalyzed Buchwald-Hartwig amination reactions was demonstrated with tunable π-acceptor bicyclic bridgehead phosphoramidite (briphos) ligands. The catalytic activity of NHC-Pd-L (L = phosphorus ligand) precatalysts depends on the electronic properties of L. A NHC-Pd-L catalyst with an N-cyclohexyl-substituted briphos ligand was found to be highly efficient. A series of C-N bond coupling reactions between primary or secondary amines and aryl chlorides were performed with high yields under mild reaction conditions.
- Kim, Miji,Shin, Taeil,Lee, Ansoo,Kim, Hyunwoo
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supporting information
p. 3253 - 3258
(2018/10/02)
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- The invention relates to a N, N - disubstituted hydrazide as ligand copper catalysis C - N coupling method (by machine translation)
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The invention discloses a to N, N - disubstituted hydrazide as ligand copper catalysis C - N coupling method, the method uses the aromatic halides with amine compound as a raw material, in order to alcohol compound as the solvent, in order to copper or copper compound as a catalyst, in order to as formula I or formula II as shown by a N, N - disubstituted hydrazide as a ligand, the presence of a base, in the 10 - 130 °C generating C - N coupled reaction for generating N - aryl compound: the invention mild reaction conditions, high chemical selectivity, substrate and wide range of application, simplicity of operation, product is simple and easy to separation and environmental protection, the obtained product yield is higher. Wherein R1, R2 is selected from methyl, phenyl, 4 - methoxyphenyl, 4 - nitro-phenyl, 2 - methylphenyl, 2 - isopropyl phenyl; R3 is hydrogen or methoxy. (by machine translation)
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Paragraph 0085
(2017/07/21)
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- Room-Temperature CuI-Catalyzed Amination of Aryl Iodides and Aryl Bromides
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A general and effective CuI/N′,N′-diaryl-1H-pyrrole-2-carbohydrazide catalyst system was developed for the amination of aryl iodides and bromides at room temperature with good chemoselectivity between -OH and -NH2 groups. Only 5 mol % of CuI and ligands was needed in this protocol to effect the amination of various aryl bromides and aryl iodides with a wide range of aliphatic and aryl amines (1.3 equiv).
- Ding, Xiaomei,Huang, Manna,Yi, Zhou,Du, Dongchen,Zhu, Xinhai,Wan, Yiqian
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p. 5416 - 5423
(2017/05/25)
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- Arylation of adamantanamines: IX. Copper(I)-catalyzed arylation of adamantane-containing amines
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Copper(I)-catalyzed arylation of 14 adamantane-containing amines with iodobenzene, 1-fluoro-4-iodobenzene, 1-iodo-4-(trifluoromethyl)benzene, and 1-iodo-4-methoxybenzene has been studied under the conditions optimized previously. The yields of the N-aryla
- Averin,Panchenko,Abel,Maloshitskaya,Butov,Savelyev,Orlinson,Novakov,Beletskaya
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p. 1788 - 1798
(2018/02/06)
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- Synthesis of Polyfunctional Secondary Amines by the Reaction of Functionalized Organomagnesium Reagents with Tertiary Nitroalkanes
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Addition of polyfunctionalized aryl, heteroaryl, and tertiary alkylmagnesium reagents to tertiary nitroalkanes at 25A"°C in tetrahydrofuran produces, after reductive workup with FeCl2 and NaBH4 in ethanol, the corresponding polyfunctional secondary amines in high yields.
- Dhayalan, Vasudevan,Knochel, Paul
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p. 3246 - 3256
(2015/10/19)
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- Synthesis of polyfunctional secondary amines by the addition of functionalized zinc reagents to nitrosoarenes
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Addition of functionalized aryl, heteroaryl or adamantyl zinc reagents to various nitroso-arenes in the presence of magnesium salts and LiCl in THF produces after a reductive work-up with FeCl2 and NaBH4 in ethanol the corresponding polyfunctional secondary amines in high yields. This journal is
- Dhayalan, Vasudevan,S?mann, Christoph,Knochel, Paul
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supporting information
p. 3239 - 3242
(2015/06/01)
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- Method of producing higher amine (by machine translation)
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PROBLEM TO BE SOLVED: To provide a method of producing a secondary or tertiary higher amine. SOLUTION: The method of producing a higher amine comprises allowing a primary or secondary amine to react with an alcohol in the presence of at least one species of hydrogen halide selected from hydrogen chloride, hydrogen bromide and hydrogen iodide, or in the presence of a compound capable of producing a hydrogen halide (such as 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride). If the raw material amine is a primary amine, a secondary higher amine and a tertiary higher amine can be produced. If the raw material amine is a secondary amine, a tertiary higher amine can be produced. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0048; 0061
(2016/10/08)
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- A synthetic and mechanistic investigation into the cobalt(i) catalyzed amination of aryl halides
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Employing first-row transition metals in catalytic two-electron transformations remains a synthetic challenge. In order to overcome the common and often deleterious single-electron reactivity, an electron rich ligand was targeted on cobalt. Herein, we report the Co(i) catalyzed amination of aryl halides with lithium hexamethyldisilazide. This transformation features (PPh3)3CoCl (1) as the catalyst and affords structurally diverse and electronically varied primary arylamines in good chemical yields, with the scope of the reaction featuring arylamines that cannot be synthesized via traditional metal-catalyzed amination routes, including 4-aminophenylboronic acid pinacol ester. Stoichiometric reactivity revealed that (PPh3)2CoN(SiMe3)2 (2) is likely generated within the catalytic cycle and could be independently synthesized from the reaction of (PPh3)3CoCl with LiN(SiMe3)2. Catalytic reactivity featuring the Co-amide complex, (PPh3)2CoN(SiMe3)2, showed that it is a competent catalyst, implying that the (PPh3)3CoCl may be serving as a pre-catalyst in the reaction. Both stoichiometric and kinetic studies support the catalytic cycle involving a Co(i) complex. Catalytic reactions featuring Co(ii) complexes resulted in undesired biaryl formation, a product that is not observed under standard catalytic conditions and any productive catalytic reactivity likely arises from an in situ reduction of Co(ii) to Co(i). A Hammett study was carried out to differentiate between a closed-shell or radical mechanism, the results of which are consistent with the proposed closed-shell mechanism. Initial studies indicate that this reactivity may be expanded to other bulky nucleophiles. This journal is
- Brennan, Marshall R.,Kim, Dongyoung,Fout, Alison R.
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p. 4831 - 4839
(2015/02/19)
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- New phosphine-functionalized NHC ligands: Discovery of an effective catalyst for the room-temperature amination of aryl chlorides with primary and secondary amines
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We report convenient and high-yielding syntheses of new phosphine-functionalized dihydroimidazolium salts and demonstrate their utility as ligand precursors for Buchwald-Hartwig amination. Several examples of the general formula [1-Mes-3-{2-(PR2)phenyl}imidazolidin-2-ylium][BF 4] have been prepared, where phosphines of varying steric and electronic properties (R = Ph (9), Cy (10), 1-Ad (11)) are tethered by an o-phenylene group. The synthesis was not adaptable to N-aryl groups other than mesityl, giving unexpected phosphonium salt species instead. The synthesis was adapted to flexible benzyl-linked variants of the formula [1-Ar-3-{2-(PCy 2)benzyl}imidazolidin-2-ylium][BF4], which allowed more steric variation of the dihydroimidazolium N-aryl group (Ar = Mes (21), Dipp (22)). A preliminary study of these hybrid NHC/P ligands in Buchwald-Hartwig amination catalysis (in situ precatalyst formation) revealed 11 to be the most active of the series. Premixing the isolated free NHC ligand 1-Mes-3-{2-(PAd2)phenyl}imidazolidin-2-ylidene (23) with [Pd(cinnamyl)Cl]2 provided a highly active precatalyst that performed well at room temperature and 1 mol % catalyst loading. The system was shown to have an unprecedented ability to arylate both primary alkylamines (monoarylation) and secondary dialkylamines with aryl chlorides at room temperature. Electron-rich and -poor aryl and heteroaryl halides, as well as those featuring ortho substitution, were well tolerated, while substrates featuring both primary and secondary amine groups were selectively arylated at the NH2 position. Furthermore, a preliminary examination of performance in ammonia arylation and acetone α-arylation showed promising results, giving good conversion and high selectivity for monoarylation in both cases.
- Wheaton, Craig A.,Bow, John-Paul J.,Stradiotto, Mark
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p. 6148 - 6161
(2013/12/04)
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- Selective N-alkylation of amines with alcohols by using non-metal-based acid-base cooperative catalysis
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Learning to cooperate: A straightforward method for the selective N-mono- and dialkylation of amines with alcohols by means of non-metal-based catalysis promoted by TAPC is reported (see scheme). Selectivity of the N-mono- and dialkylation, substrate scope and functional-group tolerance are highlighted with respect to each amine (1° and 2°; aromatic and aliphatic) and alcohol (1°, 2° and 3°; benzylic and aliphatic) component. Copyright
- Du, Ya,Oishi, Shunsuke,Saito, Susumu
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supporting information; experimental part
p. 12262 - 12267
(2011/11/29)
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- Novel acyclic diaminocarbene ligands with increased steric demand and their application in gold catalysis
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Sterically demanding and conformationally stable N,N′- ditertiaryalkyl-N,N′-diphenyl acyclic diaminocarbenes (ADCs) were developed. Bulky ADC-Au catalysts not only showed competitive reactivities in hydroamination and enyne cyclization but also demonstrat
- Seo, Hwimin,Roberts, Benjamin P.,Abboud, Khalil A.,Merz Jr., Kenneth M.,Hong, Sukwon
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supporting information; experimental part
p. 4860 - 4863
(2011/02/22)
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- Adamantyl-substituted retinoid-derived molecules that interact with the orphan nuclear receptor small heterodimer partner: Effects of replacing the 1-adamantyl or hydroxyl group on inhibition of cancer cell growth, induction of cancer cell apoptosis, and inhibition of Src homology 2 domain-containing protein tyrosine phosphatase-2 activity
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(E)-4-[3-(1-Adamantyl)-4′-hydroxyphenyl]-3-chlorocinnamic acid (3-Cl-AHPC) induces the cell-cycle arrest and apoptosis of leukemia and cancer cells. Studies demonstrated that 3-Cl-AHPC bound to the atypical orphan nuclear receptor small heterodimer partner (SHP). Although missing a DNA-binding domain, SHP heterodimerizes with the ligand-binding domains of other nuclear receptors to repress their abilities to induce or inhibit gene expression. 3-Cl-AHPC analogues having the 1-adamantyl and phenolic hydroxyl pharmacophoric elements replaced with isosteric groups were designed, synthesized, and evaluated for their inhibition of proliferation and induction of human cancer cell apoptosis. Structure-anticancer activity relationship studies indicated the importance of both groups to apoptotic activity. Docking of 3-Cl-AHPC and its analogues to an SHP computational model that was based on the crystal structure of ultraspiracle complexed with 1-stearoyl-2-palmitoylglycero-3-phosphoethanolamine suggested why these 3-Cl-AHPC groups could influence SHP activity. Inhibitory activity against Src homology 2 domain-containing protein tyrosine phosphatase 2 (Shp-2) was also assessed. The most active Shp-2 inhibitor was found to be the 3′-(3,3-dimethylbutynyl) analogue of 3-Cl-AHPC.
- Dawson, Marcia I.,Xia, Zebin,Jiang, Tao,Ye, Mao,Fontana, Joseph A.,Farhana, Lulu,Patel, Bhaumik,Li, Ping Xue,Bhuiyan, Mohammad,Pellicciari, Roberto,Macchiarulo, Antonio,Nuti, Roberto,Zhang, Xiao-Kun,Han, Young-Hoon,Tautz, Lutz,Hobbs, Peter D.,Jong, Ling,Waleh, Nahid,Chao, Wan-Ru,Feng, Gen-Sheng,Pang, Yuhong,Su, Ying
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supporting information; experimental part
p. 5650 - 5662
(2009/08/09)
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- Ligand- and Base-Free Copper(II)-Catalyzed C-N Bond Formation: Cross-Coupling Reactions of Organoboron Compounds with Aliphatic Amines and Anilines
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(Equation presented) A ligandless and base-free Cu-catalyzed protocol for the cross-coupling of arylboronic acids and potassium aryltrifluoroborate salts with primary and secondary aliphatic amines and anilines is described. The process utilizes catalytic copper(II) acetate monohydrate and 4 A molecular sieves in dichloromethane at slightly elevated temperatures under an atmosphere of oxygen. A broad range of functional groups are tolerated on both of the cross-coupling partners.
- Quach, Tan D.,Batey, Robert A.
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p. 4397 - 4400
(2007/10/03)
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- Adamantyl substituted oxindoles as pharmaceutical agents
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This invention relates to a method of treating cancer by administering a compound of the formula wherein R1, R2, R3, R4, R5, E1, E2, p, Het' and Het" are defined as indicated in
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- Adamantyl substituted oxindoles as pharmaceutical agents
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This invention relates to a method of treating cancer by administering a compound of the formula or wherein R1, R2, R3, R4, R5, E1, E2, p, Het' and Het" are defined as indicated
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- REACTION OF 1-HYDROXYADAMANTANE WITH AROMATIC AMINES IN THE PRESENCE OF ORTHO-ALKYLATION CATALYSTS
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The reaction of 1-hydroxyadamantane with aniline and N-methylaniline in the presence of hydrochlorides of the corresponding amines and aluminum anilide gives a mixture of mono- and di(1-adamantyl)anilines and 4,4'-di(1-adamantyl)diphenylamine, in which th
- Olifirov, D. I.,Koshchii, V. A.,Kozlikovskii, Ya. B.
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p. 152 - 157
(2007/10/02)
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- REACTIONS OF 1.3-DEHYDROADAMANTANE (3.3.1-PROPELLANE SYSTEM) WITH CH- AND NH-ACIDS.
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Reactions of 1.3-dehydroadamantane with aniline in the presence of its hydrochloride, p-toluenesulfamide, and malonic ester are investigated.
- Kogay, B. E.,Sokolenko, W. A.
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p. 613 - 616
(2007/10/02)
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