100-61-8Relevant articles and documents
Flash vacuum pyrolysis of 3-oxo-2-arylhydrazonopropanals and related derivatives
Ibrahim, Yehia A,Kaul, Kamini,Al-Awadi, Nouria A
, p. 10171 - 10176 (2001)
Flash vacuum pyrolysis (FVP) of 3-oxo-2-arylhydrazonopropanals at 500°C and 0.02 Torr yielded the corresponding derivatives of anilines, N-formylanilines, N-benzoylanilines and benzoylnitriles. Similar FVP of phenylhydrazonomalononitrile, phenylhydrazonoa
Oxygen activation by iron(III)-porphyrin/NaBH4/Me4N·OH system as cytochrome P-450 model. Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond
Mori,Santa,Higuchi,Mashino,Hirobe
, p. 292 - 295 (1993)
Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond were conducted with tetraphenylporphyrinatoiron(III) (Fe3+TPPCl), NaBH4, Me4N·OH, and molecular dioxygen in benzene-methanol solution. Fe3+TPPCl, NaBH4, and molecular dioxygen were essential for these reactions and the yields were decreased when Me4N·OH was absent. Olefins were converted to alcohols, which were not produced from the corresponding epoxides under the same conditions. In styrene oxygenation, an electron-donating substituent on the substrate decreased the reactivity, whereas in N,N-dimethylaniline demethylation, it enhanced the reactivity. Despite the use of the same reagents, the key intermediates of these two reactions are different. Fe2+TPP-σ-alkyl complexes produced from Fe3+TPPCl, olefin, and NaBH4 were identified as intermediates under anaerobic conditions. Fe2+TPP-σ-alkyl complex reacted with molecular dioxygen to give oxygenated products. Examination of the relative reactivities of p-substituted N,N-dimethylanilines in the NaBH4 reaction system revealed first, that the demethylation proceeded via one-electron abstraction, and second, that the reactive species of the demethylation reactions seems to be an iron-oxenoid.
First gold(I) complex-catalyzed oxidative carbonylation of amines for the syntheses of carbamates
Shi,Deng
, p. 443 - 444 (2001)
At 200 °C and 5 MPa of initial total pressure, the oxidative carbonylation of amines for the synthesis of the corresponding carbamates by Au(I) complexes as catalysts was conducted with excellent conversion and selectivity.
Heterocyclization of iminium salts from some β-amino-β-lactams and their gem-difunctional derivatives
Nisole,Uriac,Huet,Toupet
, p. 1081 - 1098 (1992)
β-Amino-β-lactams and their gem-difunctional derivatives of two series (1-benzoazepine and linear analog) lead stereospecifically to two types of heterocycles in strong acidic medium. Iminium ions and benzylic carbocations are proposed as reactive intermediates.
The design, synthesis and evaluation of selenium-containing 4-anilinoquinazoline hybrids as anticancer agents and a study of their mechanism
An, Baijiao,Zhang, Shun,Hu, Jinhui,Pan, Tingting,Huang, Ling,Tang, Johnny Cheuk-On,Li, Xingshu,Chan, Albert S. C.
, p. 4701 - 4714 (2018)
Inhibition of tubulin polymerization is one of the significant strategies in the treatment of cancer. Inspired by the excellent antitumor activity of EP128495 and the beneficial biological activities of selenium compounds, a series of new selenium-containing 4-anilinoquinazoline hybrids were synthesized and evaluated as tubulin polymerization inhibitors. An anti-proliferative activity assay showed that most of the compounds inhibited human sensitive cancer cells at low nanomolar concentrations. A mechanism study revealed that the optimal compound 5a disrupted microtubule dynamics, decreased the mitochondrial membrane potential and arrested HeLa cells in the G2/M phase, finally resulting in cellular apoptosis.
Catalysis of Anilide Ethanolysis by Barium- and Strontium - Ethoxide Pairs and Their Complexes with 18-Crown-6
Cacciapaglia, Roberta,Di Stefano, Stefano,Kelderman, Erik,Mandolini, Luigi,Spadola, Francesco
, p. 6476 - 6479 (1998)
The metal-bound ethoxide species that are quantitatively formed upon mixing equimolar amounts of Me4NOEt and alkaline-earth (Ba, Sr) metal salt in ethanol solution are more reactive than free ethoxide in the cleavage of simple activated amides (e.g. N-methyl-2,2,2-trifluoroacetanilide) lacking any donor group for binding to the metal ion. It is suggested that a metal-coordinated solvent molecule acts as a general acid catalyst for expulsion of the aniline leaving group in the rate-determining step. The position of the proton in the transition state is strongly dependent upon structural variations in the aniline portion, as suggested by the magnitude of kinetic solvent isotope effects. Enhanced catalysis is observed upon addition of equimolar amounts of 18-crown-6, which is tentatively interpreted on the basis of the notion that ion pairing is weakened upon cation binding to a crown ether. Important differences concerning metal ion effects in amide vs ester cleavage are pointed out and discussed on the basis of results obtained upon structural modifications of the substrates.
Oxoiminium Ions for N-Demethylation: 1-Oxo-2,2,6,6,-tetramethylpiperidinium Chloride
Hunter, Duncan H.,Racok, Julie S.,Rey, Allan W.,Ponce, Yolanda Zea
, p. 1278 - 1281 (1988)
In an attempt to assess the synthetic utylity of oxoiminium ions as oxidizing agents and to delineate their reaction mechanisms, we reacted 1-oxo-2,2,6,6-tetramethylpiperidinium chloride (1) with several N,N-dialkylanilines.With N,N-dimethylaniline the only basic product was N-nethylaniline while N- methylformanilide was the only neutral product.The relative amounts of base and neutral product proved to be sensitive to the amount of water present in the reaction medium.With N-alkyl-N-methylanilines, the basic products were N-alkylanilines from exlusive loss of the N-methyl group.The neutral products were the N-alkylformanilides.The alkyl groups studied were ethyl, n-butyl, isopropyl, and benzyl.With N-tert-butyl-N-methylaniline, there was no observed reaction, and N,N-diethylaniline was found to be significantly less reactive than N,N-dimethylaniline.This study has shown that 1 is selective in N-demethylation of anilines in the presence of other alkyl groups either on the same nitrogen or on separate nitrogens.These results have been interpreted in terms of important steric interactions resulting from formation of an adduct en route to an intermediate iminium ion.
Reduction of hydrazines, azo and azoxy compounds, and amine N-oxides with the NiCl2·2H2O-Li-DTBB (cat.) combination
Alonso, Francisco,Radivoy, Gabriel,Yus, Miguel
, p. 8673 - 8678 (2000)
The NiCl2·2H2O/Li/DTBB (10 mol%) combination allows the reduction of aromatic hydrazines 1 (to amines), azo compounds 2 (to primary amines), azoxy compounds 3 (to azo compounds or to primary amines, depending on the reaction conditions) or amine N-oxides 4 (to tertiary amines), under mild reaction conditions (THF, room temperature). (C) 2000 Elsevier Science Ltd.
Synthesis of N-Methylaniline and N,N-Dimethylaniline with Methanol over Alumina Catalyst
Matsuhashi, Hiromi,Arata, Kazushi
, p. 2605 - 2606 (1991)
Alumina catalysts prepared by different methods were used for the synthesis of N-methylaniline and N,N-dimethylaniline from aniline and methanol.Al2O3 catalysts prepared from isopropoxide and nitrate showed high activity and JRC-ALO-1 and JRC-ALO-3 supplied by the Catalysis Society of Japan showed low activity.The highest selectivity for N,N-dimethylaniline was 82.8percent with 90.1percent aniline conversion.The catalytic activity of Al2O3 was not poisoned by pyridine and CO2.
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Coats,Katritzky
, p. 1836 (1959)
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Scandium ion-enhanced oxidative dimerization and N -demethylation of N, N -dimethylanilines by a non-heme iron(IV)-oxo complex
Park, Jiyun,Morimoto, Yuma,Lee, Yong-Min,You, Youngmin,Nam, Wonwoo,Fukuzumi, Shunichi
, p. 11612 - 11622 (2011)
Oxidative dimerization of N,N-dimethylaniline (DMA) occurs with a nonheme iron(IV)-oxo complex, [FeIV(O)(N4Py)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), to yield the corresponding dimer, tetramethylbenzidine (TMB), in acetonitrile. The rate of the oxidative dimerization of DMA by [FeIV(O)(N4Py)]2+ is markedly enhanced by the presence of scandium triflate, Sc(OTf)3 (OTf = CF3SO3-), when TMB is further oxidized to the radical cation (TMB?+). In contrast, we have observed the oxidative N-demethylation with para-substituted DMA substrates, since the position of the C-C bond formation to yield the dimer is blocked. The rate of the oxidative N-demethylation of para-substituted DMA by [FeIV(O) (N4Py)]2+ is also markedly enhanced by the presence of Sc(OTf) 3. In the case of para-substituted DMA derivatives with electron-donating substituents, radical cations of DMA derivatives are initially formed by Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, giving demethylated products. Binding of Sc3+ to [FeIV(O)(N4Py)]2+ enhances the Sc3+ ion-coupled electron transfer from DMA derivatives to [Fe IV(O)(N4Py)]2+, whereas binding of Sc3+ to DMA derivatives retards the electron-transfer reaction. The complicated kinetics of the Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+ are analyzed by competition between binding of Sc3+ to DMA derivatives and to [FeIV(O)(N4Py)] 2+. The binding constants of Sc3+ to DMA derivatives increase with the increase of the electron-donating ability of the para-substituent. The rate constants of Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, which are estimated from the binding constants of Sc3+ to DMA derivatives, agree well with those predicted from the driving force dependence of the rate constants of Sc3+ ion-coupled electron transfer from one-electron reductants to [FeIV(O)(N4Py)]2+. Thus, oxidative dimerization of DMA and N-demethylation of para-substituted DMA derivatives proceed via Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+.
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Grandjean et al.
, p. 207,210 (1976)
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Alkylation of aniline with methanol in the presence of FeCl 3·6H2O in carbon tetrachloride
Khusnutdinov,Bayguzina,Aminov
, p. 1447 - 1450 (2013)
The reaction of aniline with methanol in the presence of FeCl 3·6 H2O in carbon tetrachloride leads to the formation of N-methyl- and N,N-dimethylanilines and 4,4′-methylenebis(N,N- dimethylaniline).
CuCl2-catalyzed one-pot formation of tetrahydroquinolines from N-methyl-N-alkylanilines and vinyl ethers in the presence of t-butylhydroperoxide
Yang, Xianghua,Xi, Chanjuan,Jiang, Yanfeng
, p. 978 - 987 (2006)
Tetrahydroquinoline skeletons can be formed by a CuCl2-catalyzed one-pot reaction of N-methyl-N-alkylanilines and vinyl ethers in the presence of t-butylhydroperoxide.
Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO2for consecutiveN-methylation of amines
Das, Arpan,Maji, Subir,Mandal, Swadhin K.
, p. 12174 - 12180 (2021)
A mesoionic N-heterocyclic olefin (mNHO) was introduced as a metal-free catalyst for the reductive functionalization of CO2leading to consecutive doubleN-methylation of primary amines in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN). A wide range of secondary amines and primary amines were successfully methylated under mild conditions. The catalyst sustained over six successive cycles ofN-methylation of secondary amines without compromising its activity, which encouraged us to check its efficacy towards doubleN-methylation of primary amines. Moreover, this method was utilized for the synthesis of two commercially available drug molecules. A detailed mechanistic cycle was proposed by performing a series of control reactions along with the successful characterisation of active catalytic intermediates either by single-crystal X-ray study or by NMR spectroscopic studies in association with DFT calculations.
N-Methylation of amine and nitro compounds with CO2/H2 catalyzed by Pd/CuZrOx under mild reaction conditions
Cui, Xinjiang,Zhang, Yan,Deng, Youquan,Shi, Feng
, p. 13521 - 13524 (2014)
An active Pd/ZrCuOx catalyst was prepared for the reductive amination of CO2. The N-methylation of amines and nitro compounds with CO2/H2 can be realized with up to 97% yield under relatively mild reaction condi
Distinguishing Rate-Limiting Electron versus H-Atom Transfers in Cu 2(O2)-Mediated Oxidative N-Dealkylations: Application of Inter- versus Intramolecular Kinetic Isotope Effects
Shearer, Jason,Zhang, Christiana Xin,Hatcher, Lanying Q.,Karlin, Kenneth D.
, p. 12670 - 12671 (2003)
Copper-dioxygen adducts are important biological oxidants. To gain a better understanding of the underlying chemistries of such species, we report on a series of Cu2II-O2 complexes, [{CuII(MePY2)R-}2(O2)](B(C6F5)4)2 (1R-) (where (MePY2)R- is a 4-pyridyl substituted bis[2-(2-(4-R-pyridyl)ethyl]methylamine; R- = H, MeO, Me2N; Zhang, C. X.; et al. J. Am. Chem. Soc. 2003, 125, 634-635), which readily oxidize exogenous substrates. In this study, we explore the mechanism by which 1R- facilitates the oxidative N-dealkylation of para-substituted N,N-dimethylanilines (R-DMA; R = MeO, Me, H, CN). In the case of 1H, the linear free-energy correlation plot (ρ = -2.1) and intramolecular deuterium kinetic isotope effect (KIEintra, using p-R-(C6H4)-N(CH3)(CD3)) profile suggest that R-DMA oxidation occurs through rate-limiting electron transfer (ET). This mechanism was further enforced by comparison of KIEintra versus the intermolecular KIE (KIEinter, using p-R-(C6H4)-N(CH3)2 versus p-R-(C6H4)-N(CD3)2). It was found that KIEinter intra, suggesting an ET process. In the case of both 1MeO and 1Me2N, the KIEintra profile and linear free-energy correlation plots (ρ = -0.49 and -0.99 for 1Me2N and 1MeO with especially poor fitting for the latter) are inconclusive in distinguishing between a rate-limiting ET or hydrogen atom transfer (HAT) pathway. Comparisons of KIEinter versus KIEintra demonstrate a switch in mechanism from ET to HAT for 1Me2N and 1MeO oxidation of R-DMA as R-DMA is made less reducing. In the case of 1Me2N, MeO-DMA and Me-DMA are oxidized via a rate-limiting ET (KIEinter intra), while H-DMA and CN-DMA are oxidized through a HAT pathway (KIEinter ≈ KIEintra). For 1MeO, oxidation occurs through an ET pathway for MeO-, Me-, and H-DMA (KIEinter intra), while CN-DMA is oxidized though a HAT process (KIEinter ≈ KIEintra). Copper complex attributes, which may contribute to the mechanistic observations, are suggested. Copyright
Continuous acid-catalyzed methylations in supercritical carbon dioxide: Comparison of methanol dimethyl ether and dimethyl carbonate as methylating agents
Gooden, Peter N.,Bourne, Richard A.,Parrott, Andrew J.,Bevinakatti, Han S.,Irvine, Derek J.,Poliakoff, Martyn
, p. 411 - 416 (2010)
The development of high-yielding, "greener" chemistry-based routes for the continuous synthesis of methyl ethers are reported in this study. Ethers have been efficiently produced using a methodology which eliminates the use of toxic alkylating agents and reduces the waste generation that is characteristic of traditional etherification processes. For the first time it is shown that the use of acidic heterogeneous catalysts can successfully achieve etherification when using scCO2 as a reaction medium. Furthermore, the relative efficiencies of three alternative methylating agents, dimethyl carbonate, dimethyl ether and MeOH, have been compared and contrasted for the methylation of 1-octanol. Dimethyl carbonate has proven to be the superior methylating agent, demonstrating higher conversion and selectivity. Successful methylation of secondary alcohols, diols, carboxylic acids and amines using dimethyl carbonate in supercritical carbon dioxide has also been shown. Substrate structure was found to influence the temperature required to maximize the yield of the desired product, substrates with multiple hydroxyl groups requiring the highest temperatures.
Ruthenium-Catalyzed N-Alkylation and N-Benzylation of Aminoarenes with Alkohols
Watanabe, Yoshihisa,Tsuji, Yasushi,Ige, Hitoshi,Ohsugi, Yukihiro,Ohta, Tetsuo
, p. 3359 - 3363 (1984)
Aminoarenes were readily converted into secondary and tertiary amines by the reaction at 150-180 deg C with primary alcohols in the presence of a catalytic amount (1 mol percent based on the aminoarene) of a ruthenium complex.Dichlorotris(triphenylphosphine)ruthenium was the most effective catalyst precursor.Secondary amines were obtained in excellent yields when aminoarenes reacted with an equimolar amount of alcohols.With excess alcohols, tertiary amines were obtained predominantly.Kinetic measurements revealed that the rate had zero-order dependence on aminoarene concentration and first-order dependence on alcohol concentration and initial concentration of the ruthenium catalyst.From the kinetic features, the possible catalytic cycle, which includes the nucleophilic attack of the aminoarene on aldehyde intermediate, was postulated.
N-(α-Aminoalkyl)benzotriazoles: Novel "Nonstabilized" α-Aminocarbanion Synthons
Katritzky, Alan R.,Qi, Ming,Feng, Darning,Nichols, Daniel A.
, p. 4121 - 4124 (1997)
C-Benzotriazole bonds were selectively transformed to give the corresponding α-aminocarbanions when N-(α-aminoalkyl)benzotriazoles were reacted with either Li/LiBr or SmI2 in the presence of representative electrophiles. The ranges of applicability of the two reagents complement each other, and together the two protocols provide a general route from readily available crystalline starting materials to a variety of "nonstabilized" α-aminocarbanions that can be trapped in moderate to good yields.
Absolute kinetics of aminium radical reactions with olefins in acetonitrile solution
Wagner, Brian D.,Ruel, Géraldine,Lusztyk, Janusz
, p. 13 - 19 (1996)
Photolysis of N-nitrosamines in acidic acetonitrile produces aminium radical cations via protonation of the initially-formed aminyl radicals. The kinetics of these species can be monitored by transient UV spectroscopy via their absorption band which is found at ca. 300 nm in the case of the piperidinium radical, for example. By measuring the aminium radicals' lifetimes as a function of the concentration of added olefin, absolute values for the bimolecular rate constants for the addition reactions were obtained. In the case of the piperidinium radical, these rate constants varied from 6 M-1 s-1 for acrylonitrile to 1.1 ± 0.1 × 109 M-1 s-1 for 1,1-diphenylethylene and generally increased with decreasing ionization potential of the olefin, thus confirming the electrophilic nature of the piperidinium radical. The rate constants for analogous reactions of diethylaminium radicals were 1.5-25 times smaller indicating the importance of steric factors in aminium radical additions to olefins. The rate constant for the intramolecular 1,5-addition of the secondary aminium radical cation to an unactivated double bond is estimated to be ca. 1 × 106 s-1, but the intramolecular addition rate constant increases to >1 × 108 s-1 upon the phenyl substitution at the olefinic terminus.
A general and convenient procedure for the synthesis of N- alkylarylamines and N-alkylheteroarylamines by electrophilic amination of cuprates with N-alkylhydroxylamines
Bernardi, Paolo,Dembech, Pasquale,Fabbri, Gaia,Ricci, Alfredo,Seconi, Giancarlo
, p. 641 - 643 (1999)
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Methylation of secondary amines with dialkyl carbonates and hydrosilanes catalysed by iron complexes
Zheng, Jianxia,Darcel, Christophe,Sortais, Jean-Baptiste
, p. 14229 - 14232 (2014)
Methylation of secondary amines was achieved using dimethyl carbonate or diethyl carbonate as the C1 source under the catalysis of well-defined half-sandwich iron complexes bearing an N-heterocyclic carbene ligand. The reaction proceeded under mild conditions in the presence of hydrosilanes as the reductants, and the amines were obtained with good to excellent isolated yields. This journal is
Zinc oxide surface: a versatile nanoplatform for solvent-free synthesis of diverse isatin derivatives
Kothandapani, Jagatheeswaran,Ganesan, Asaithampi,Mani, Ganesh Kumar,Kulandaisamy, Arockia Jayalatha,Rayappan, John Bosco Balaguru,Selva Ganesan, Subramaniapillai
, p. 3472 - 3475 (2016)
Multicomponent reactions performed on the surface of nanostructured zinc oxide gave 3,3-bis(indolyl)indolin-2-one and xanthene derivatives with excellent yields. Both Lewis acidic (Zn2+) and basic (O2?) sites on the surface of zinc oxide were utilized to perform the aforementioned transformations. The significance of surface catalysis was further proved by performing the experiment with surface masked zinc oxide. The developed zinc oxide nanocatalyst was reusable up to five times without significant loss in its activity.
Mono-N-methylation of primary amines with alkyl methyl carbonates over Y faujasites. 2. Kinetics and selectivity
Selva, Maurizio,Tundo, Pietro,Perosa, Alvise
, p. 9238 - 9247 (2002)
In the presence of a Na-exchanged Y faujasite, the reaction of primary aromatic amines 1 with 2-(2-methoxyethoxy)methylethyl carbonate [MeO(CH2)2O(CH2)2 OCO2Me, 2a] yields the corresponding mono-N-methyl derivatives ArNHMe with selectivity up to 95%, at substantially quantitative conversions. At 130°C, the reaction can be run under diffusion-free conditions and is strongly affected by the solvent polarity: for instance, in going from xylene (εr = 2.40) to triglyme (εr = 7.62) as the solvent, the pseudo-first-order rate constant for the aniline (1a) disappearance shows a 5-fold decrease. In DMF (εr = 38.25), the same reaction does not occur at all. Competitive adsorption of the solvent and the substrate onto the catalytic sites accounts for this result. The behavior of alkyl-substituted anilines ZC6H4NH2 [Z = p-Me, p-Et, p-Pr, p-(n-Bu) (1b-e); Z = 3,5-di-tert-butyl- and 2,4,6-tri-tert-butylanilines (1f,g)] and p-alkoxyanilines p-ZC6H4NH2 [Z = OMe, OEt, OPr, O-n-Bu (1b′-e′)] clearly indicates a steric effect of ring substituents: as diffusion of the amine into the catalytic pores is hindered, the reaction hardly proceeds and the mono-N-methyl selectivity (SM/D) drops as well. Moreover, the strength of adsorption of the amine onto the catalyst influences the rate and the selectivity as well: the reaction of p-anisidine and p-toluidine - despite the higher nucleophilicity of these compounds - is slower and even less selective with respect to aniline. From a mechanistic viewpoint, the intermediacy of carbamates ArN(Me)CO2R [R = MeO-(CH2)2O(CH2)2] is suggested. At 90°C, the reaction of benzylamine (7) - a model for aliphatic amineswith dimethyl carbonate shows that the reaction outcome can be improved by tuning the amphoteric properties of the catalyst: in going from CsY to the more acidic LiY zeolite, methylation is not only more selective (SM/D ratio increases from 77% to 84%) but even much faster (CsY, conversion of 36% after 22 h; LiY, conversion of 43% after 7 h).
Green and chemo selective amine methylation using methanol by an organometallic ruthenium complex
Abbasi, Alireza,Dindar, Sara,Nemati Kharat, Ali
, (2021/11/16)
Herein a green and convenient catalytic N-methylation of aniline and n-hexylamine using methanol as a dual methylation agent and solvent has been investigated. A new ruthenium carbonyl complex was synthesized and applied as a homogeneous catalyst in methylation reaction. The solid-state structure of the complex was determined by X-ray crystallographic analysis which indicate xantphos ligand bonded to ruthenium (II) as a tridentate pincer ligand by two P donor and one O atom. The catalytic system showed excellent conversion and selectivity toward N-methylaniline, and N,N-hexyldimethylamine at 140°C.
Copper(i)-catalysed intramolecular hydroarylation-redox cross-dehydrogenative coupling ofN-propargylanilines with phosphites
Li, Guangzhe,Yu, Guo,Wang, Chengdong,Morita, Taiki,Zhang, Xuhai,Nakamura, Hiroyuki
supporting information, p. 113 - 116 (2021/12/29)
Intramolecular hydroarylation-redox cross-dehydrogenative coupling ofN-propargylanilines with phosphite diesters proceeded in the presence of Cu(i)-catalysts (20 mol%) to selectively give 2-phosphono-1,2,3,4-tetrahydroquinolines in good yields with 100% atomic utilization. P-H and two C-H bonds are activated at once and these hydrogen atoms are trapped by a propargylic triple bond in the molecule.
K2S2O8-induced site-selective phenoxazination/phenothiazination of electron-rich anilines
Lei, Aiwen,Wang, Pengjie,Wang, Shengchun,Wang, Xiaoyu,Yi, Hong,Zhang, He,Zhang, Heng
supporting information, p. 147 - 151 (2022/01/19)
By just using cheap K2S2O8 as the oxidant at room temperature in the air, the phenoxazination/phenothiazination of electron-rich anilines to construct or modify triarylamine derivatives has been established. This method demonstrates complete para-selective amination under catalyst-free conditions and its simplicity and efficiency lead to good performance in flow-chemistry synthesis.
