30438-95-0Relevant academic research and scientific papers
DMSO-allyl bromide: A mild and efficient reagent for atom economic one-pot: N -allylation and bromination of 2°-aryl amines, 2-aryl aminoamides, indoles and 7-aza indoles
Kannadasan, Sathananthan,Novanna, Motakatla,Shanmugam, Ponnusamy,Smile, Suresh Snoxma
, p. 1834 - 1839 (2022/02/07)
A mixture DMSO-allyl bromide has been developed as a reagent for an atom economic one-pot N-allylation and aryl bromination under basic conditions. Utilizing this reagent, N-allylation-bromination of a number of 2°-aryl amines, aryl aminoamides, indoles, and 7-aza indoles has been achieved. The scope of the substrates and limitations, the synthetic utility of the products, and a plausible reaction mechanism have been proposed.
Spin Delocalization, Polarization, and London Dispersion Forces Govern the Formation of Diradical Pimers
Ellern, Arkady,Peterson, Joshua P.,Winter, Arthur H.
supporting information, p. 5304 - 5313 (2020/04/08)
Some free radicals are stable enough to be isolated, but most are either unstable transient species or exist as metastable species in equilibrium with a dimeric form, usually a spin-paired sigma dimer or a pi dimer (pimer). To gain insight into the different modes of dimerization, we synthesized and evaluated a library of 15 aryl dicyanomethyl radicals in order to probe what structural and molecular parameters lead to σ- versus π-dimerization. We evaluated the divergent dimerization behavior by measuring the strength of each radical association by variableerature electron paramagnetic resonance spectroscopy, determining the mode of dimerization (σ- or π-dimer) by UV-vis spectroscopy and X-ray crystallography, and performing computational analysis. We evaluated three different hypotheses to explain the difference in the dimerization behavior: (1) that the dimerization behavior is dictated by radical spin densities; (2) that it is dictated by radical polarizability; (3) that it is dictated by London dispersion stabilization of the pimer. However, no single parameter model in itself was predictive. Two-parameter models incorporating either the computed degree of spin delocalization or the radical polarizability as well as computed estimates for the attractive London dispersion forces in the π-dimers lead to improved forecasts of σ- vs π-dimerization mode, and suggest that a balance of spin delocalization of the isolated radical as well as attractive forces between the stacked radicals, govern the formation of diradical pimers.
Sequential Oxidative α-Cyanation/Anti-Markovnikov Hydroalkoxylation of Allylamines
Wagner, Alexander,Hampel, Nathalie,Zipse, Hendrik,Ofial, Armin R.
supporting information, p. 4770 - 4773 (2015/10/12)
Iron-catalyzed oxidative α-cyanations at tertiary allylamines in the allylic position are followed by anti-Markovnikov additions of alcohols across the vinylic CC double bonds of the initially generated α-amino nitriles. These consecutive reactions generate 2-amino-4-alkoxybutanenitriles from three reactants (allylamines, trimethylsilyl cyanide, and alcohols) in one reaction vessel at ambient temperature.
Highly selective N-allylation of anilines under microwave irradiation
Liu, Meiyu,Wang, Xie,Sun, Xiaoliang,He, Wei
, p. 2711 - 2714 (2014/05/06)
An easy and rapid procedure for the preparation of a variety of mono- and bis-allylated anilines via the reaction of allyl bromide with a wide range of anilines under microwave irradiation is described. This approach allows use of mild conditions and short reaction times to give high selectivities and excellent yields.
BENZAMIDE TRPA1 ANTAGONISTS
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Page/Page column 33, (2014/12/12)
Compounds of formula I, pharmaceutically acceptable salts thereof, diastereomers, enantiomers, or mixtures thereof: wherein R, X, Y, Z, n and A are as defined in the specification, as well as pharmaceutical compositions including the compounds are prepared. They are useful in therapy, in particular in the management of pain.
Silica-functionalized CuI: An efficient and selective catalyst for N-benzylation, allylation, and alkylation of primary and secondary amines in water
Shamim, Tahira,Kumar, Vineet,Paul, Satya
, p. 620 - 632 (2014/01/17)
Silica-functionalized CuI has been reported as an efficient and selective catalyst for the selective mono-N- and N,N-dibenzylation, allylation, and alkylation of primary amines with benzylic, allylic, and alkyl halides using NaOH as base in aqueous medium. By changing the reaction temperature, mono- or di-benzylation, allylation, or alkylation could be achieved in good yield and selectivity. Secondary amines have also been benzylated, allylated, and alkylated under similar conditions. SiO2-CuI has been characterized by Fourier transform-infrared, atomic absorption spectrometry, thermalgravimetric analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, and found to be highly selective and recyclable under the reaction conditions. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.] Copyright
Synthesis and characterization of N-phenyl pyrrole anchored to Fischer carbene complex through ring closing metathesis oxidative aromatization and various aryl substituted Fischer carbene complexes
Ganesamoorthi,Thakur, Arunabha,Sharmila,Ramkumar,Ghosh, Sundargopal
, p. 56 - 61 (2013/03/13)
Ring closing metathesis of pentacarbonyl[(ethoxy)(N,N-diallyl anilyl)carbene]tungsten(0) complex, [(CO)5W=C(OCH2CH 3)C6H4N(CH2CHCH2) 2], 1 leads to the formation of pentacarbonyl[(ethoxy)(N-phenyl 2,5-dihydro pyrrolyl)carbene]tungsten(0) complex, [(CO)5W=C(OCH 2CH3)C6H4N (CH2CHCH 2)2], 2 in good yield. Further, complex 2 undergoes oxidative aromatization to afford N-phenyl pyrrole anchored to alkoxy carbene, 3. In addition, a number of aryl substituted carbene complexes [(CO) 5W=C(OCH2CH3)C6H4R], 4-7 (4: R = OCH2CH3; 5: R = OCH2CH=CH2; 6: R = OCH=CHCH2CH2CH2CH2CH 3; 7: OC6H5Br) have been synthesized from the reaction of 1-(allyloxy)-4-bromobenzene with W(CO)6 in presence of various concentration of n-BuLi and Meerwein's salt. All the complexes have been isolated in moderate to good yields and have been characterized by 1H NMR, 13C NMR, IR, UV-vis spectroscopic techniques and the solid state structures of 1, 2 and 4 have been unequivocally established by X-ray diffraction analysis.
Copper-catalyzed electrophilic amination of arylsilanes with hydroxylamines
Miki, Yuya,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
supporting information, p. 172 - 175 (2013/03/28)
A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl] dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.
Copper-catalyzed amination of arylboronates with N,N-dialkylhydroxylamines
Matsuda, Naoki,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
, p. 3642 - 3645 (2012/05/20)
A tolerant coupling: The title reaction has been developed to deliver arylamines (see scheme; Bz=benzoyl, dppbz=1,2-bis(diphenylphosphino)benzene). The catalysis is based on electrophilic, umpolung amination and enables the use of secondary acyclic amines. Various functional groups are tolerated, thus opening up a new substrate class for the Chan-Lam-type coupling.
Sequential combination of ruthenium-, base-, and gold-catalysis - A new approach to the synthesis of medicinally important heterocycles
Ramachary, Dhevalapally B.,Narayana, Vidadala V.
supporting information; experimental part, p. 3514 - 3522 (2011/08/06)
A general approach to the high-yielding synthesis of medicinally important heterocycles was achieved through the sequential combination of ring-closing metathesis, base-induced ring opening (BIRO), hydroamination, and a Diels-Alder reaction of functionalized allyl-(2-allylphenyl)amines in the presence of a catalytic amount of Grubbs' second-generation catalyst, base (tBuOK), and [AuCl(PPh3)]/AgOTf. Herein, we also demonstrate the important electronic factors in the BIRO of N-substituted-benzo[b]azepines for the regioselective synthesis of functionalized (Z)-N-substituted-2-(buta-1,3-dienyl) phenylamines in very good yields with high purity; these are very good, useful compounds in medicinal chemistry. We also discovered the selective cascade synthesis of privileged hexahydrophenanthridines from (Z)-N-substituted-2-(buta- 1,3-dienyl)phenylamines by gold catalysis in moderate to good yields with >99 % diastereomeric excess. The possible reaction mechanism for the unusual hydroamination followed by [4+2] cycloaddition of functionalized (Z)-N-substituted-2-(buta-1,3-dienyl)phenylamines through gold catalysis is discussed in this work. A novel process for the synthesis of highly substituted, medicinally important heterocycles was achieved through the sequential combination of ring-closing methathesis, base-induced ring opening, hydroamination, and Diels-Alder reaction of functionalized allyl-(2-allylphenyl) amines in the presence of a catalytic amount of [Ru], base, and [Au] (see scheme). Copyright
