- Low-Temperature Intramolecular [4+2] Cycloaddition of Allenes with Arenes for the Synthesis of Diene Ligands
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The intramolecular [4+2] cycloaddition between arenes and allenes first reported by Himbert gives rapid access to rigid polycyclic scaffolds. Herein, we report a one-pot oxyalkynylation/cycloaddition reaction proceeding under mild conditions (23–90 °C) an
- Hari, Durga Prasad,Pisella, Guillaume,Wodrich, Matthew D.,Tsymbal, Artem V.,Tirani, Farzaneh Fadaei,Scopelliti, Rosario,Waser, Jerome
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supporting information
p. 5475 - 5481
(2021/01/21)
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- N-heterocyclic carbene copper(i) catalysed N-methylation of amines using CO2
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The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(i) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.
- Santoro, Orlando,Lazreg, Fama,Minenkov, Yury,Cavallo, Luigi,Cazin, Catherine S. J.
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p. 18138 - 18144
(2015/10/28)
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- Selective monomethylation of primary amines with simple electrophiles
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Direct monomethylation of primary amines with methyl triflate was achieved with high selectivity (up to 96%). The key point of this single methyl transfer stems from the use of HFIP as the solvent that interferes with amines and avoids overmethylation.
- Lebleu, Thomas,Ma, Xiaolu,Maddaluno, Jacques,Legros, Julien
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supporting information
p. 1836 - 1838
(2014/02/14)
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- Palladium-catalyzed amidation by chemoselective C(sp3)-H activation: Concise route to oxindoles using a carbamoyl chloride precursor
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Quite select: A new strategy was developed for the synthesis of various oxindoles from carbamoyl chlorides. Under the optimum reaction conditions, with Ad2PBu as a ligand, tBuCONHOH as an additive, and a CO atmosphere, selective C(sp3/sup
- Tsukano, Chihiro,Okuno, Masataka,Takemoto, Yoshiji
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supporting information; experimental part
p. 2763 - 2766
(2012/05/05)
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- INDAZOLEPROPIONIC ACID AMIDE COMPOUND
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Disclosed is a compound which is useful in preventing and treating cardiac arrhythmia such as atrial fibrillation. A compound represented by formula (1) or a pharmaceutically acceptable salt of the same. In formula (1), ring X represents benzene or pyridine; R1 represents an optionally substituted alkyl group; R2 represents an optionally substituted aryl group, an optionally substituted heterocyclic group, an optionally substituted arylalkyl group or an optionally substituted heterocyclic group-substituted alkyl group; R3, R4, R5, R6, R7, R8 and R9 represent each hydrogen or an alkyl group, provided that R3 and R5 may be bonded to each other to form, together with the carbon atom adjacent thereto, a cycloalkyl group; and m represents 0 or 1.
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Page/Page column 37
(2012/02/01)
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- Half-titanocence anilide complexes Cp′TiCl2[N(2,6-R 12C6H3)R2]: Synthesis, structures and catalytic properties for ethylene polymerization and copolymerization with 1-hexene
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A number of new half-sandwich titanium(IV) complexes of the type [Cp′TiCl2{N(2,6-R12C6H 3)R2}] [R1 = iPr (1, 2, 4), Me (3, 5); R 2 = Me (1, 3, 4, 5), Bn (2); Cp′ = Cp
- Liu, Kefeng,Wu, Qiaolin,Gao, Wei,Mu, Ying,Ye, Ling
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experimental part
p. 1901 - 1909
(2011/06/24)
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- Substituent effects on aromatic stacking interactions
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Synthetic supramolecular zipper complexes have been used to quantify substituent effects on the free energies of aromatic stacking interactions. The conformational properties of the complexes have been characterised using NMR spectroscopy in CDCl3, and by comparison with the solid state structures of model compounds. The structural similarity of the complexes makes it possible to apply the double mutant cycle method to evaluate the magnitudes of 24 different aromatic stacking interactions. The major trends in the interaction energy can be rationalised using a simple model based on electrostatic interactions between the π-faces of the two aromatic rings. However, electrostatic interactions between the substituents of one ring and the π-face of the other make an additional contribution, due to the slight offset in the stacking geometry. This property makes aromatic stacking interactions particularly sensitive to changes in orientation as well as the nature and location of substituents. This journal is The Royal Society of Chemistry.
- Cockroft, Scott L.,Perkins, Julie,Zonta, Cristiano,Adams, Harry,Spey, Sharon E.,Low, Caroline M. R.,Vinter, Jeremy G.,Lawson, Kevin R.,Urch, Christopher J.,Hunter, Christopher A.
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p. 1062 - 1080
(2007/12/27)
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- Selective mono-N-methylation of primary aromatic amines by dimethyl carbonate over faujasite X- and Y-type zeolites
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The reaction of dimethyl carbonate (DMC) with different primary aromatic amines has been investigated under batch conditions (autoclave) in the presence of Y- and X-type zeolites. Operating at 120-150°C, highly selective mono-N-methylations are observed for anilines even when they are deactivated by either electronic effects or steric hindrance (G-C6H4NH2, G = p-NO2,p-CN, o-CO2CH3 and 2,6-dimethylaniline); typical selectivities for the formation of the corresponding mono-N-methyl derivatives [ArNH(CH3)] are in the range 92-98%, at a substrate conversion of 72-93%. A synergic effect between the reactivity of DMC (acting both as a methylating and as a reversible methoxycarbonylating agent) and the dual acid-base properties of zeolites is considered to be responsible for the unusually high selectivity observed; accordingly, a reaction mechanism is discussed, involving carbamates (ArNHCO2CH3) and N-methyl-carbamates [ArN(CH3)CO2CH3] as intermediates. The reaction is an example of a synthesis with low environmental impact: it couples the use of a non-toxic methylating agent (DMC, in place of the highly toxic methyl halides or dimethyl sulfate) with eco-friendly catalysts (zeolites) in a waste-free process.
- Selva, Maurizio,Bomben, Andrea,Tundo, Pietro
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p. 1041 - 1045
(2007/10/03)
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- Tyrosine kinase inhibitors. 3. Structure-activity relationships for inhibition of protein tyrosine kinases by nuclear-substituted derivatives of 2,2'-dithiobis(1-methyl-N-phenyl-1H-indole-3-carboxamide)
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A series of indole-substituted 2,2'-dithiobis(1-methyl-N-phenyl-1H- indole-3-carboxamides) were prepared and evaluated for their ability to inhibit the tyrosine kinase activity of both the epidermal growth factor receptor (EGFR) and the nonreceptor pp60(v-src) tyrosine kinase. The compounds were synthesized by conversion of appropriate 1-methyloxindoles to 1-methyl-2-indolinethiones with P2S5 followed by subsequent reaction with NaH and phenyl isocyanate and oxidative dimerization of the resulting 2,3- dihydro-N-phenyl-2-thioxo-1H-indole-3-carboxamides. The parent compound and many of the substituted analogues were moderately potent inhibitors of both kinase enzymes, but no clear relationships were seen between substitution on the indole ring and inhibitory activity. While 4-substituted compounds were generally inactive, 5-substituted derivatives with electron-withdrawing groups showed inhibitory activity. However, none of the substituted compounds showed significantly better activity than the unsubstituted parent compound. There was generally a good correlation between activity against the EGFR and pp60(v-src) kinases, but several compounds did show some specificity (>20- fold) of inhibition; 5-Cl and 5-Br derivatives preferentially inhibited pp60(v-src), while the 5-CF3 compound preferentially inhibited EGFR. Selected compounds from the series were found to inhibit the growth of Swiss 3T3 fibroblasts with IC50s in the range 2-25 μM, the most active being 4- substituted derivatives. The compounds inhibited bFGF-mediated protein tyrosine phosphorylation in intact cells more effectively than EGFR- or PDGF- mediated phosphorylation.
- Rewcastle,Palmer,Dobrusin,Fry,Kraker,Denny
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p. 2033 - 2042
(2007/10/02)
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- LITHIATION ROUTES TO OXINDOLES AND 2-INDOLINETHIONES: PRECURSORS TO 2,2'-DITHIOBISINDOLES WITH TYROSINE KINASE INHIBITORY PROPERTIES
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N-Substituted oxindoles and 2-indolinethiones can be prepared by lithiation of carboxyl protected N,2-dimethylanilines followed by quenching with CO2 or CS2 respectively. 2-Indolinethione derivatives are also available via demethylation of 2-methylthioindoles, which are prepared by lithiation of N-substituted indoles and treatment with dimethyl disulfide.
- Rewcastle, Gordon W.,Denny, William A.
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p. 701 - 708
(2007/10/02)
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- Cycloadditions, 16. - Influence of Alkyl and Phenyl Groups in the Allenic ω-Position on the Intramolecular Diels-Alder Reactions of Allene Carbamides
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The influences of methyl (partly of other alkyl) and phenyl moieties in the allenic ω-position on the isomerization tendencies of the N-phenyl- and N-(α-naphthyl)allenecarboxamides (5, 6 and 7, 8, resp.) are investigated.Methyl groups always decelerate (5, 7, 8 -> 9, 10, 11a-c), phenyl groups hinder (5f -> 9f and 12f), prevent (5, 6g), or accelerate (7f,g, 8g -> 10f,g, 11g) the intramolecular Diels-Alder reactions.The diphenyl compounds 5g, 6g cyclize to give the quinolones 12, 13; if this cyclization is prevented by two methyl groups in the ortho positions (s. 15), the common dimerization of allenes takes place to give the cyclobutane derivative 17. - Key Words: Allenecarboxamides/ Diels-Alder reaction/ Dimerization
- Himbert, Gerhard,Diehl, Klaus,Schlindwein, Hans-Juergen
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p. 1691 - 1700
(2007/10/02)
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- Revisitation of Formaldehyde Aniline Condensation. VIII. - Monomeric N-Methylene Anilines
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A convenient, high yield "dry" method of synthesis of monomeric N-methyleneanilines (6a-i) and the characterization of the products by m.s., 1H- and 13C-n.m.r. and i.r. are reported, improving previous procedures and describing new compounds.It appeared that the existence of monomeric N-methyleneanilines is stricly related to the presence of enough steric hindrance to oligomerization by substituents in ortho positions.Moreover, some addition products of formaldehyde to an amine and its corresponding imines are tentatively identified on the basis of the observed mass spectrum of the whole reaction mixture.The reaction products of formaldehyde with 2,6-dimethylaniline (1a) provided an example of a mobile equilibrium between monomeric and trimeric imine.
- Giumanini, Angelo G.,Verardo, Giancarlo,Polana, Marco
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p. 161 - 174
(2007/10/02)
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- A HIGHLY EFFICIENT AND GENERAL N-MONOMETHYLATION OF FUNCTIONALIZED PRIMARY AMINES VIA FORMYLATION -- BORANE:METHYL SULFIDE REDUCTION
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Formylation of functionalized primary aromatic and aliphatic amines with acetic formic anhydride (AFA) followed by borane:methyl sulfide reduction in the same pot affords the corresponding N-methylamines in excellent isolated yields, uncontaminated by bis alkylation; the reaction sequence is applicable to even very weakly basic and sterically hindered amines.
- Krishnamurthy, S.
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p. 3315 - 3318
(2007/10/02)
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- Process for the production of (substituted) 2,6-dimethylanilines
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Aniline derivatives of the formula STR1 wherein R is hydrogen, C1 -C4 -alkyl or C1 -C4 -alkyl substituted by C1 -C2 -alkoxy are produced by reacting a N-(3-pent-2-enyl)-derivative of morpholine, piperidine or pyrrolidine with acrolein in the presence of an inert, aprotic solvent or in the absence of a solvent and heating the reaction product obtained to 100°-400° C. in the presence of a hydrogen-transfer catalyst and in the presence of an amine of the formula R--NH2, wherein R has the meaning given above.
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