- Selective Synthesis of Primary Anilines from NH3 and Cyclohexanones by Utilizing Preferential Adsorption of Styrene on the Pd Nanoparticle Surface
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Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH3 and cyclohexanones. However, the selective synthesis of primary anilines is quite difficult because the desired primary aniline products and the cyclohexanone substrates readily undergo condensation affording the corresponding imines (i.e., N-cyclohexylidene-anilines), followed by hydrogenation to produce N-cyclohexylanilines as the major products. In this study, primary anilines were selectively synthesized in the presence of supported Pd nanoparticle catalysts (e.g., Pd/HAP, HAP=hydroxyapatite, Ca10(PO4)6(OH)2) by utilizing competitive adsorption unique to heterogeneous catalysis; in other words, when styrene was used as a hydrogen acceptor, which preferentially adsorbs on the Pd nanoparticle surface in the presence of N-cyclohexylidene-anilines, various structurally diverse primary anilines were selectively synthesized from readily accessible NH3 and cyclohexanones. The Pd/HAP catalyst was reused several times though its catalytic performance gradually declined.
- Koizumi, Yu,Jin, Xiongjie,Yatabe, Takafumi,Miyazaki, Ray,Hasegawa, Jun-ya,Nozaki, Kyoko,Mizuno, Noritaka,Yamaguchi, Kazuya
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supporting information
p. 10893 - 10897
(2019/07/12)
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- Pd-tBuONO Cocatalyzed Aerobic Indole Synthesis
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A Pd-tBuONO co-catalyzed scalable and practical synthesis of indoles with molecular oxygen as terminal oxidant is developed. Either terminal or internal 2-vinylanilines could be smoothly converted to desired indoles under one general condition. This method has been evaluated in the large scale synthesis of indomethacin and a potential anti-breast cancer drug candidate 1. (Figure presented.).
- Ning, Xiao-Shan,Liang, Xin,Hu, Kang-Fei,Yao, Chuan-Zhi,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 1590 - 1594
(2018/04/30)
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- Selenium-catalyzed oxidative c(sp2)-h amination of alkenes exemplified in the expedient synthesis of (Aza-)indoles
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A new selenium-catalyzed protocol for the direct, intramolecular amination of C(sp2)-H bonds using N-fluorobenzenesulfonimide as the terminal oxidant is reported. This method enables the facile formation of a broad range of diversely functionalized indoles and azaindoles derived from easily accessible ortho-vinyl anilines and vinylated aminopyridines, respectively. The procedure exploits the pronounced carbophilicity of selenium electrophiles for the catalytic activation of alkenes and leads to the formation of C(sp2)-N bonds in high yields and with excellent functional group tolerance.
- Ortgies, Stefan,Breder, Alexander
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supporting information
p. 2748 - 2751
(2015/06/16)
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- Highly Diastereo- and Enantioselective CuH-Catalyzed Synthesis of 2,3-Disubstituted Indolines
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A diastereo- and enantioselective CuHcatalyzed method for the preparation of highly functionalized indolines is reported. The mild reaction conditions and high degree of functional group compatibility as demonstrated with substrates bearing heterocycles,
- Ascic, Erhad,Buchwald, Stephen L.
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supporting information
p. 4666 - 4669
(2015/04/27)
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- A new entry to the phenanthridine ring system
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A new synthesis of phenanthridine derivatives having three-point diversity has been developed based on the sequential application of three-atom economic processes viz. aza-Claisen rearrangement, ring-closing enyne metathesis and Diels-Alder reaction as key steps. An unexpected isomerisation was observed during aza-Claisen rearrangement of N-allylanilines which may open up new opportunities in heterocyclic synthesis.
- Mondal, Poulomi,Thander, Latibuddin,Chattopadhyay, Shital K.
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p. 1328 - 1331
(2012/04/04)
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- Pd-catalyzed arylation/ring-closing metathesis approach to azabicycles
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Palladium-catalyzed arylation followed by Grignard addition to imines and ring-closing metathesis, using Grubbs' catalysts, provides a route to six-, seven-, and eight-membered azabicycles.
- Martínez-Estíbalez, Unai,Sotomayor, Nuria,Lete, Esther
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p. 2919 - 2922
(2008/02/03)
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- New pathway to the synthesis of substituted 4H-3,1-benzoxazines
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The intramolecular rearrangement of N-acyl-2-cyclopropylanilines by the action of protic acids gives substituted 4H-3,1-benzoxazines. The reaction proceeds in high yield through the formation of benzoxazine precursors, namely, the corresponding 3,1-benzoxazinium ions, which are stable in acid solution. N-Acylamino-2-alkenylbenzenes, in which the double bond of the alkyl chain is conjugated with the benzene ring, are capable of undergoing a similar rearrangement.
- Mochalov,Gazzaeva,Fedotov,Shabarov,Zefirov
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p. 794 - 801
(2007/10/03)
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- Pyrolyses of o-Alkoxy- and o-Alkylthio-N-Allylanilines and of Some Related O- and S-Allyl Compounds
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The o-substituted allyl compounds (1)-(12) have been pyrolysed in order to generate aminyl, phenoxyl, and thiophenoxyl radicals with adjacent substituents.In all cases, products are formed by intramolecular hydrogen transfer from the substituent to the radical centre.This process may be followed by rearrangement to give an aldehyde, by heteroatom extrusion to give an alkene, or by ring formation to give five-membered ring heterocycles (Scheme 1, routes A, B1, and B2 respectively.The distribution of products formed by each route is dependent both on the nature of the o-substituent, and on the nature of the initial radical.
- Cadogan, J. I. G.,Hickson, Clare L.,McNab, Hamish
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p. 1885 - 1890
(2007/10/02)
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- Fluxionality in (cyclohtptatriene)iron tricarbonyl complexes
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1H NMR spin saturation transfer experiments were undertaken to measure the barrier for 1,3 iron shifts in (cyclobeptatriene)iron tricarbonyl (CHT = cycloheptatriene) complexes.
- Karel, Karin J.
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p. 419 - 430
(2008/10/08)
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- Intramolecular 1,1-Cycloaddition of Nitrilimines as a Route to Benzodiazepines and Cyclopropacinnolines
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Treatment of o-vinylphenyl-substituted chloroglyoxylate phenylhydrazones with base leads to nitrilimines.These reactive 1,3-dipoles undergo intramolecular 1,1-cycloaddition with complete retention of configuration to give cyclopropacinnolines.When the
- Padwa, Albert,Nahm, Steven
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p. 1402 - 1409
(2007/10/02)
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- Photochemical Synthesis. Conversion of o-Vinylthioanilides to Quinolines
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Quinoline derivatives are formed in fair to good yields when acetonitrile solutions of o-vinylthioanilides are irradiated with Pyrex-filtered light.The transformation is a singlet reaction and involves intramolecular cycloaddition of the thioamide, yielding unstable thietanes, as the initial step.In the case of o-(1-trans-propenyl)thioacetanilide (2a) the corresponding thietane has been detected by 1H NMR spectroscopy by irradiating a toluene solution of the compound at -78 deg C.The quantum yield of quinoline formation from 2a appeared to be solvent dependent.Concomitant with quinoline formation, triplet cis-trans isomerization of the vinyl moiety takes place.In the case of 2a the quantum yield for trans -> cis isomerization is 0.506.A variable-temperature 1H NMR study of 2,3-dimethylquinoline in toluene solution has also been performed.For the 2,3-dimethylquinoline-toluene complex the enthalpy and entropy of formation are -1.03 +/- 0.10 kcal/mol and -3.7 +/- 0.2 gibbs/mol, respectively.
- Mayo, Paul de,Sydnes, Leiv K.,Wenska, Grazyna
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p. 1549 - 1556
(2007/10/02)
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- METAL COMPLEXES WITH ALLYLANILINES. IV. SYNTHESIS AND REACTIVITY OF RHODIUM(I) COMPLEXES WITH 2-ALLYLANILINE AND N-ALLYLANILINE
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The reaction of 2-allylaniline (2aa) with 2 (I) in toluene or benzene at room temperature affords the dimer 2 (II) in which the ligand acts as bidentate, being coordinated to the metal through the N atom and the olefinic group.II in CH2Cl2, isomerizes 2aa to trans-2-propenylaniline.This reaction goes also catalytically.Heating of II in benzene affords 2-methyl-indoline.N-Allylaniline (naa) reacts with I to give the deep violet diamagnetic complex Rh2Cl2(naa)3 (III), which is converted slowly into 2.When III is heated with an excess of naa, the ligand is catalytically transformed into propene, azobenzene, N-n-propylaniline, N-i-propylaniline, N-allylideneaniline and aniline, as the more abundant products.Moreover, III reacts with diphenylacetylene to afford 2,5-dihydro-1,2,3-triphenyl-4-methyl-pyrrole.The reaction of III with methylacetylene follows a more complex path, and products of dimerization and trimerization of the alkyne have been isolated.Carbon dioxide influences the oligomerization reaction.
- Aresta, M.,Fazio, M. De
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p. 109 - 120
(2007/10/02)
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