- The first aza Diels-Alder reaction involving an α,β-unsaturated hydrazone as the dienophile: Stereoselective synthesis of C-4 functionalized 1,2,3,4-tetrahydroquinolines containing a quaternary stereocenter
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The reaction between aromatic imines and methacrolein dimethylhydrazone in the presence of 10% indium trichloride affords in good to excellent yields biologically and synthetically relevant 1,2,3,4-tetrahydroquinolines bearing a hydrazone function at C-4 in a one-pot process that involves the formation of two C-C bonds and the stereoselective generation of two stereocenters, one of them quaternary, and this constitutes the first example of an α,β-unsaturated dimethylhydrazone behaving as a dienophile in a hetero Diels-Alder reaction and the first vinylogous aza-Povarov reaction. This journal is The Royal Society of Chemistry.
- Sridharan, Vellaisamy,Perumal, Paramasivan T.,Avendano, Carmen,Menendez, J. Carlos
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- A novel water-dispersible and magnetically recyclable nickel nanoparticles for the one-pot reduction-Schiff base condensation of nitroarenes in pure water
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In this work, a heterogeneous nanocatalyst called Ni-Fe3O4@Pectin~PPA ~ Piconal was first synthesized, which was investigated as a bifunctional catalyst containing nickel functional groups. On the other hand, this Ni-Fe3O4@Pectin~PPA ~ Piconal catalyst in aqueous solvents shows a very effective performance at ambient temperature for the nitroarene reduction reaction with sodium borohydride, for which NaBH4 is considered as a reducing agent. This is a novelty magnetic catalyst that was approved by various methods, including Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), Dynamic light scattering (DLS), Transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), Inductively coupled plasma (ICP), Energy-dispersive X-ray spectroscopy (EDX), and Field emission scanning electron microscopy (FESEM) analyses. From the satisfactory results obtained from the reduction of nitrogen, this catalytic system is used for a one-pot protocol containing a reduction-Schiff base concentration of diverse nitroarenes. It was corroborated with the heterogeneous catalytic experiments on the one-pot tandem synthesis of imines from nitroarenes and aldehydes. Finally, the novel Ni-Fe3O4@Pectin~PPA ~ Piconal catalyst could function as a more economically desirable and environmentally amicable in the catalysis field. The favorable products are acquired in good to high performance in the attendance of Ni-Fe3O4@Pectin~PPA ~ Piconal as a bifunctional catalyst. This catalyst can be recycled up to six steps without losing a sharp drop.
- Ghamari Kargar, Pouya,Ravanjamjah, Asiye,Bagherzade, Ghodsieh
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p. 1916 - 1933
(2021/07/10)
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- Application of a catalyst-free Domino Mannich/Friedel-Crafts alkylation reaction for the synthesis of novel tetrahydroquinolines of potential antitumor activity
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A useful and efficient method to construct diversely substituted 1,2,3,4-tetrahydroquinolines in good to excellent yields has been developed through a catalyst-free Domino Mannich and intramolecular Friedel-Crafts alkylation reactions of N-arylamines with
- Castillo, Juan-Carlos,Jiménez, Elizabeth,Portilla, Jaime,Insuasty, Braulio,Quiroga, Jairo,Moreno-Fuquen, Rodolfo,Kennedy, Alan R.,Abonia, Rodrigo
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p. 932 - 947
(2018/02/09)
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- Iron-Catalyzed Reductive Ethylation of Imines with Ethanol
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The borrowing hydrogen strategy has been applied to the ethylation of imines with an air-stable iron complex as precatalyst. This approach opens new perspectives in this area as it enables the synthesis of unsymmetric tertiary amines from readily available substrates and ethanol as a C2 building block. A variety of imines bearing electron-rich aryl or alkyl groups at the nitrogen atom could be efficiently reductively alkylated without the need for molecular hydrogen. The mechanism of this reaction, which shows complete selectivity for ethanol over other alcohols, has been studied experimentally and by means of DFT computations.
- Vayer, Marie,Morcillo, Sara P.,Dupont, Jennifer,Gandon, Vincent,Bour, Christophe
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supporting information
p. 3228 - 3232
(2018/03/13)
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- Higher Order Constitutional Dynamic Networks: [2×3] and [3×3] Networks Displaying Multiple, Synergistic and Competitive Hierarchical Adaptation
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The present study investigates the constitutional dynamic networks (CDNs) underlying dynamic covalent libraries (DCLs) that extend beyond the [2×2] case toward higher orders, namely [2×3] and [3×3] CDNs involving respectively six and nine constituents generated from the recombination of five and six components linked through reversible chemical reactions. It explores the behavior of such systems under the action of one or two effectors. More specifically and for the sake of proof of principle, it makes use of DCLs involving dynamic organic ligands and analyzes their single and double adaptive response under the action of one and two metal cation effectors. Thus, interconversions within [2×3] DCLs of six constituents (hydrazone, acylhydrazone, and imine ligands) give access to the generation of [2×3] CDNs of 3D trigonal prismatic type consisting of three [2×2] sub-networks and presenting specific responses to the application of Cu+ and Zn2+ metal cation effectors, in particular double agonistic amplification. More complex [3×3] CDNs based on nine ligand constituents of imine, hydrazone, and acylhydrazone types were also designed and subjected to the application of one or two effectors, e.g., Cu+ and Fe2+ metal cations, revealing novel types of adaptive behavior: (i) agonistic amplification between a single constituent and a full [2×2] sub-network, and (ii) agonistic amplification along a single diagonal connecting three constituents. Of special interest is also the dependence of the response of the system to hierarchical sequence of effector application, whereby initial interaction with Cu+ ions results in the destruction of the network, whereas the sequence Fe2+ followed by Cu+ yields a clean three-constituent DCL. Finally and strikingly, the present results also demonstrate that the increase in complexity of the system by introduction of an additional entity leads to a simpler output through dynamic competition between components.
- Men, Guangwen,Lehn, Jean-Marie
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supporting information
p. 2474 - 2483
(2017/02/23)
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- Synthesis and biological evaluation of new fluconazole β-lactam conjugates linked via 1,2,3-triazole
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Novel 1,2,3-triazole-linked β-lactam-fluconazole conjugates 12(a-l) were designed and synthesized. The compounds showed potent antifungal activity against two pathogenic Candida strains; Candida albicans ATCC 24433 and Candida albicans ATCC 10231 with MIC values in the range of 0.0625-2 μg mL-1. Compounds 12h, 12j and 12k showed promising antifungal activity against all the tested fungal pathogens except C. neoformans ATCC 34554 compared to fluconazole. Compound 12j in which the β-lactam ring was formed using para-anisidine and benzaldehyde was found to be more potent than fluconazole against all the fungal strains with an IC50 value of -1 for Candida albicans (ATCC 24433). Mechanistic studies for active compounds revealed that the antifungal action was due to ergosterol inhibition. Compounds 12h and 12j at a concentration of 0.125 μg mL-1 caused 91.5 and 96.8% ergosterol depletion, respectively, compared to fluconazole which at the same concentration caused 49% ergosterol depletion. The molecular docking study revealed that all the fluconazole β-lactam conjugates 12(a-l) could snugly fit into the active site of lanosterol 14α-demethylase (CYP51) with varying degrees of affinities. As anticipated, the binding energy for compound 12j (-58.961 kcal mol-1) was much smaller than that for fluconazole (-52.92 kcal mol-1). The synthesized compounds have therapeutic potential for the control of candidemia.
- Divse, Jaisingh M.,Mhaske, Santosh B.,Charolkar, Chaitanya R.,Sant, Duhita G.,Tupe, Santosh G.,Deshpande, Mukund V.,Khedkar, Vijay M.,Nawale, Laxman U.,Sarkar, Dhiman,Pore, Vandana S.
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supporting information
p. 470 - 479
(2017/02/05)
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- Quinone-catalyzed oxidative deformylation: Synthesis of imines from amino alcohols
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A new method for imine synthesis by way of quinone-catalyzed oxidative deformylation of 1, 2-amino alcohols is reported. A wide range of readily accessible amino alcohols and primary amines can be reacted to provide N-protected imine products. The methodology presented provides a novel organocatalytic approach for imine synthesis and demonstrates the synthetic versatility of quinone-catalyzed oxidative C-C bond cleavage.
- Liu, Xinyun,Phan, Johnny H.,Haugeberg, Benjamin J.,Londhe, Shrikant S.,Clift, Michael D.
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supporting information
p. 2895 - 2901
(2018/01/17)
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- Combination of Enabling Technologies to Improve and Describe the Stereoselectivity of Wolff-Staudinger Cascade Reaction
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A new, single-mode bench-top resonator was evaluated for the microwave-assisted flow generation of primary ketenes by thermal decomposition of α-diazoketones at high temperature. A number of amides and β-lactams were obtained by ketene generation in situ and reaction with amines and imines, respectively, in good to excellent yields. The preferential formation of trans-configured β-lactams was observed during the [2+2] Staudinger cycloaddition of a range of ketenes with different imines under controlled reaction conditions. Some insights into the mechanism of this reaction at high temperature are reported, and a new web-based molecular viewer, which takes advantage from Augmented Reality (AR) technology, is also described for a faster interpretation of computed data.
- Musio,Mariani,?liwiński,Kabeshov,Odajima,Ley
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supporting information
p. 3515 - 3526
(2016/10/18)
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- Ruthenium-catalyzed double-fold C-H tertiary alkoxycarbonylation of arenes using di-tert-butyl dicarbonate
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An efficient ruthenium-catalyzed double-fold C-H alkoxycarbonylation of arenes was developed using di-tert-butyl dicarbonate as the tertiary esterification reagent, which leads to a direct route to valuable 2,6-dicarboxylated products. This journal is
- Hong, Xiaohu,Wang, Hao,Liu, Bingxin,Xu, Bin
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supporting information
p. 14129 - 14132
(2014/12/11)
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- Oxazolidine synthesis by complementary stereospecific and stereoconvergent methods
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Complementary stereospecific and stereoconvergent reactions for enantioselective synthesis of 1,3-oxazolidines are reported. In the presence of a rhodium catalyst, reaction of enantioenriched butadiene monoxide with aryl imines is stereospecific (99% ee). Alternatively, the reaction of racemic butadiene monoxide, in the presence of a chiral palladium or nickel catalyst, provides an enantioselective synthesis of 1,3-oxazolidines (up to 94% ee). Synthesis of either the cis- or trans-1,3-oxazolidines is also accomplished under catalyst control.
- Shaghafi, Michael B.,Grote, Robin E.,Jarvo, Elizabeth R.
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supporting information; experimental part
p. 5188 - 5191
(2011/12/15)
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- Substituted Isoquinolinones and Quinazolinones
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The invention relates to substituted nitrogen containing bicyclic heterocycles of the formula (I) wherein Z is CH2 or N—R4 and X, R1, R2, R4, R6, R7 and n are as defined in the description. Such compounds are suitable for the treatment of a disorder or disease which is mediated by the activity of MDM2 and/or MDM4, or variants thereof.
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Page/Page column 68
(2011/10/10)
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- Asymmetric synthesis of indolines through intramolecular shifting of aromatic sulfinyl groups. Role of the π,π-stacking interactions in these unusual SNAr processes
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Cyclization of N-aryl substituted 1-aryl-2[2-p-tolylsulfinyl]phenyl propylamines under LDA, LHMDS, or KHMDS provides a new approach for synthesizing optically pure 2,3-disubstituted indolines. Both the scope and the limitations of this method have been investigated. The π,π-stacking interactions are crucial for these unprecedented intramolecular SNAr processes, in which a sulfinyl group located on a slightly deactivated ring is substituted by amide anions under mild conditions. X-ray and NMR proofs supporting these π,π-stacking interactions are presented.
- Ruano, Jose L. Garcia,Parra, Alejandro,Marcos, Vanesa,Del Pozo, Carlos,Catalan, Silvia,Monteagudo, Silvia,Fustero, Santos,Poveda, Ana
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supporting information; experimental part
p. 9432 - 9441
(2009/12/06)
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- Palladium-catalyzed, one-pot, three-component synthesis of homoallylic amines from aldehydes, anisidine, and allyl trifluoroacetate
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(Chemical Equation Presented) An allylation reaction that generates homoallylic amines using allyl trifluoroacetate as a nucleophilic allylmetal precursor is reported. A palladium complex catalyzes two transformations in one pot: formation of allylsilane
- Grote, Robin E.,Jarvo, Elizabeth R.
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supporting information; experimental part
p. 485 - 488
(2009/07/18)
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- An asymmetric nitro-Mannich reaction applicable to alkyl, aryl, and heterocyclic imines
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A protocol for the enantioselective nitro-Mannich coupling between alkyl, aryl, and heterocyclic p-methoxybenzylimines and trimethylsilylnitropropanate catalyzed by a chiral tBu-BOX Cu(II) catalyst is described. It uses the lowest reported load
- Anderson, James C.,Howell, Gareth P.,Lawrence, Ron M.,Wilson, Claire S.
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p. 5665 - 5670
(2007/10/03)
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- Application of erythro-2-amino-1,2-diphenylethanol as a highly efficient chiral auxiliary. highly stereoselective staudinger-type β-lactam synthesis using a 2-chloro-l-methylpyridinium salt as the dehydrating agent
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The Staudinger-type reaction of carboxylic acids with imines, using a 2-chloro-l-methylpyridinium salt as the dehydrating reagent, proceeded smoothly under mild conditions to afford the desired β-lactams in high yields with excellent cis-selectivity. This
- Matsui, Satoshi,Hashimoto, Yukihiko,Saigo, Kazuhiko
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p. 1161 - 1166
(2007/10/03)
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- Further Studies of the Kinetic Template Effect in the Metal Ion-catalysed Reactions of ortho-Donor-substituted Aryl Halides with Tertiary Phosphines. Structural Requirements of the Template
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The reactions of a series of Schiff's bases, derived from ortho-chloro-, bromo- or iodo-benzaldehydes and p-anisidine, with tertiary phosphines in the presence of nickel(II) bromide in refluxing ethanol proceed with displacement of the ortho-halogen to form the related ortho-substituted arylphosphonium salts.These reactions appear to be examples of a kinetic template effect in which the Schiff's base moiety aids the catalytic role of the metal ion in promoting the substitution reaction.Introduction of a second donor atom into the substituent group present at the nitrogen of related Schiff's bases inhibits the reactions due to diversion of the metal ion in other modes of coordination.The reactions are also inhibited by steric crowding at the imino-nitrogen.A range of other aryl halides bearing ortho-substituents having the potential to act as co-ordination templates has been prepared and their reactions with phosphines in the presence of metal ions studied enabling the rather critical nature of effective template groups to be defined.Detailed 13C n.m.r. data are also reported for the Schiff's bases and related arylphosphonium salts.
- Allen, David W.,Cropper, Paul E.,Smithurst, Peter G.,Ashton, Peter R.,Taylor, Brian F.
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p. 1989 - 1994
(2007/10/02)
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- DIPOLE MOMENTS, ESCA, THEORETICAL CALCULATIONS AND GAS-LIQUID CHROMATOGRAPHIC STUDIES ON SOME P-P prime -DERIVATIVES OF BENZYLIDENE ANILINE.
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Pairs of nematic liquid crystals of the Schiff's base type that are identical in length-to-breadth ratios, but differ in the location of the atoms in the central linkage were synthesized. Combined ESCA and theoretical calculations revealed that the nature
- Janini,Hovakeemian,Katrib,Fitzpatrick,Attari
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p. 271 - 280
(2007/10/02)
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