- N-alkylation of α-iminophosphonates and application to Horner-Wadsworth-Emmons reaction
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N-Alkylation of α-iminophosphonates with Grignard reagents gives α-N-alkylaminophosphonates. A subsequent Horner-Wadsworth-Emmons reaction of the intermediary α-metalated phosphonate takes place with aldehydes to give enamines. The enamine thus prepared reacts with MVK to give a four-component coupling product.
- Shimizu, Makoto,Tateishi, Masasato,Mizota, Isao
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- Studies towards the design and synthesis of novel 1,5-diaryl-1h-imidazole-4-carboxylic acids and 1,5-diaryl-1h-imidazole-4-carbohydrazides as host ledgf/p75 and hiv-1 integrase interaction inhibitors
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Two targeted sets of novel 1,5-diaryl-1H-imidazole-4-carboxylic acids 10 and carbohy-drazides 11 were designed and synthesized from their corresponding ester intermediates 17, which were prepared via cycloaddition of ethyl isocyanoacetate 16 and diarylimi
- Bode, Moira L.,Fish, Muhammad Q.,Mabel Coyanis, E.,Rashamuse, Thompho J.
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- Synthesis of Imidoyl Chlorides Using Phosphorus Trichloride
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Abstract: The reaction of carboxamides with phosphorus trichloride under heating at 75–80°C for 1 h in the presence of a 4-dimethylaminopyridine catalyst was used to synthesize imidoyl chlorides in yields of 63–99%.
- Nguyen, T. L.,Popov, Yu. V.,Shishkin, E. V.,Shishkin, V. E.,Vo, T. L. Q.,Zotov, Yu. L.
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p. 849 - 851
(2021/06/12)
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- Synthesis of Nitrogen-Containing Polyaromatics by Aza-Annulative π-Extension of Unfunctionalized Aromatics
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Nitrogen-containing polycyclic aromatic compounds (N-PACs) are an important class of compounds in materials science. Reported here is a new aza-annulative π-extension (aza-APEX) reaction that allows rapid access to a range of N-PACs in 11–84 % yields from readily available unfunctionalized aromatics and imidoyl chlorides. In the presence of silver hexafluorophosphate, arenes and imidoyl chlorides couple in a regioselective fashion. The follow-up oxidative treatment with p-chloranil affords structurally diverse N-PACs, which are very difficult to synthesize. DFT calculations reveal that the aza-APEX reaction proceeds through the formal [4+2] cycloaddition of an arene and an in situ generated diarylnitrilium salt, with sequential aromatizations having relatively low activation energies. Transformation of N-PACs into nitrogen-doped nanographenes and their photophysical properties are also described.
- Itami, Kenichiro,Ito, Hideto,Kawahara, Kou P.,Matsuoka, Wataru
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supporting information
p. 6383 - 6388
(2020/03/13)
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- α-Imino Iridium Carbenes from Imidoyl Sulfoxonium Ylides: Application in the One-Step Synthesis of Indoles
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Imidoyl sulfoxonium ylides are presented for the first time as potential precursors to generate α-imino metal-carbene intermediates and applied in direct C-H functionalization reactions catalyzed by [Ir(cod)Cl]2 (4 mol %) to provide 2-substituted indoles (up to 70% yield) in just one step. This class of sulfur ylide is successfully obtained from imidoyl chloride and dimethylsulfoxonium methylide (23 new examples in 45-85% yield) or by imino group formation from the corresponding β-keto sulfoxonium ylides and anilines in the presence of TiCl4 as a Lewis acid (9 examples in 33-94% yield).
- Burtoloso, Antonio C. B.,Caiuby, Clarice A. D.,De Jesus, Matheus P.
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p. 7433 - 7445
(2020/06/27)
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- Silver-Catalyzed Cascade Cyclization Reaction of Isocyanides with Sulfoxonium Ylides: Synthesis of 3-Aminofurans and 4-Aminoquinolines
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A silver-catalyzed cascade cyclization reaction of isocyanides with sulfoxonium ylides has been developed for the first time. This reaction provides a new and efficient method for the construction of highly functionalized 3-aminofurans and 4-aminoquinolines from readily available starting materials in a single step.
- Liang, Yong-Xin,Yang, Ming,He, Bo-Wen,Zhao, Yu-Long
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supporting information
p. 7640 - 7644
(2020/10/09)
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- Silver(II) oxide-mediated synthesis of 2,4-diarylquinazolines
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A single-pot procedure for the synthesis of 2,4-diarylquinazolines is described which involves a silver oxide-mediated C–H activation/C–N bond formation process. The generality of this method with respect to substituent effects is presented along with studies leading to process optimization. Mechanistic investigations provide support for the involvement of radical intermediates in the reaction process.
- Cheung, Wing,Patch, Raymond J.,Player, Mark R.
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supporting information
p. 2368 - 2371
(2018/05/25)
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- Proton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters
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This contribution presents a full account of experimental and theoretical/computational investigations into the N-heterocyclic carbene (NHC)-catalyzed proton-transfer polymerization (HTP) that converts common dimethacrylates (DMAs) containing no protic gr
- Hong, Miao,Tang, Xiaoyan,Falivene, Laura,Caporaso, Lucia,Cavallo, Luigi,Chen, Eugene Y.-X.
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supporting information
p. 2021 - 2035
(2016/03/01)
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- Solvent/oxidant-switchable synthesis of multisubstituted quinazolines and benzimidazoles via metal-free selective oxidative annulation of arylamidines
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A fast and simple divergent synthesis of multisubstituted quinazolines and benzimidazoles was developed from readily available amidines, via iodine(III)-promoted oxidative C(sp3)-C(sp2) and C(sp 2)-N bond formation in nonpolar and polar solvents, respectively. Further selective synthesis of quinazolines in polar solvent was realized by TEMPO-catalyzed sp3C-H/sp2C-H direct coupling of the amidine with K2S2O8 as the oxidant. No metal, base, or other additives were needed.
- Lin, Jian-Ping,Zhang, Feng-Hua,Long, Ya-Qiu
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supporting information
p. 2822 - 2825
(2014/06/23)
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- Synthesis of chlorinated bicyclic C-fused tetrahydrofuro[3,2- c ]azetidin-2-ones
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Some bicyclic C-fused chlorinated tetrahydrofuro[3,2-c]azetidin-2-ones were prepared by a fairly general route involving Staudinger reaction of allylic/propargylic imidates with dichloroketene followed by highly diastereoselective CuCl/PMDETA-catalyzed 5-
- Ram, Ram N.,Kumar, Neeraj,Singh, Nem
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supporting information; experimental part
p. 7408 - 7411
(2011/02/22)
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- Palladium-catalyzed cyclocarbonylation of o-lodoanilines with Imidoyl Chlorides to produce quinazolin-4(3H)-ones
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A wide variety of substituted quinazolin-4(3H)-ones were prepared in 63-91% yields by the palladium-catalyzed cyclocarbonylation of o-iodoanilines with imidoyl chlorides and carbon monoxide. The reaction is believed to proceed via in situ formation of an amidine, followed by oxidative addition, CO insertion, and intramolecular cyclization to give the substituted quinazolin-4(3H)-ones.
- Zheng, Zhaoyan,Alper, Howard
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supporting information; experimental part
p. 829 - 832
(2009/04/07)
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- Synthesis and Biological Evaluation of 2,3,5-Substituted [1,2,4]Thiadiazoles as Allosteric Modulators of Adenosine Receptors
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A number of 2,3,5-substituted [1,2,4]thiadiazole analogues of SCH-202676 (N-(2,3-diphenyl-[1,2,4]thiadiazole-5(2H)-ylidene)methanamine, 7a) were synthesized and tested as potential allosteric modulators of adenosine receptors. All compounds were capable of displacing the binding of the radiolabeled agonist [3H]CCPA to human A1 adenosine receptors, whereas modest and varying effects were observed on the binding of [3H]DPCPX, a radiolabeled antagonist for this receptor subtype. Four compounds, 7a (SCH-202676), 7k (LUF5792), 71 (LUF5794), and 8e (LUF5789), were selected for more detailed characterization. They all proved allosteric inhibitors of agonist binding, with 7k being most potent, whereas their effects on antagonist binding were more ambiguous. Subsequently, experiments were done on human adenosine A2A and A3 receptors. Compounds 7a and 7l displayed peculiar displacement characteristics of both radiolabeled agonist and antagonist binding to A2A receptors, whereas 7a showed some activity on A3 receptors.
- Van Den Nieuwendijk, Adrianus M. C. H.,Pietra, Daniele,Heitman, Laura,G?bly?s, Anikó,IJzerman, Adriaan P.
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p. 663 - 672
(2007/10/03)
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- Amidine derived 1,3-diazabuta-1,3-dienes as potential antibacterial and antifungal agents
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Several 1-aryl-2-phenyl-4-piperidino-4-thioalkyl-1,3-diazabuta-1,3-dienes were prepared by the treatment of N-arylimino isothiocyanate with piperidine followed by S-alkylation with alkyl iodides in the presence of dry acetone and potassium hydroxide. The
- Bedi, Preet M.S.,Mahajan, Mohinder P.,Kapoor, Vijay K.
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p. 3821 - 3824
(2007/10/03)
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- N-arylbenzonitrilium ions. Photochemical generation and effect of substituents in the phenyl rings on lifetimes in water and reactivity with azide ion
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Nitrilium ions Ar-C≡N+-Ar′ have been studied by laser flash photolysis in aqueous solutions containing 20% acetonitrile. The cations were generated by photoheterolysis of benzimidate esters Ar-CZ=N-Ar′ (Z = -OC6H4-4-CN) with 4-cyanophenoxide as the photochemical leaving group. Rate constants for the reaction with water (kw), azide ion (kaz) and hydroxide (kOH) were measured. The cation Ph-C≡N+-Ph is only 50-fold shorter lived in water compared to Ph-C≡N+-iPr (2); thus the effect of replacing an N-alkyl group with N-phenyl is modest. These two cations are also shown to have similar lifetimes to iminium analogs, e.g. Ph-CH=N+ (Me)-Ph. Thus, addition of water to analogous sp and sp2 hybridized systems occurs at a similar rate, and the increased steric access to the nitrilium plays at most a modest role. For the series where substituents in Ar′ were varied with Ar equal to phenyl, the Hammett plot for log kw correlated with σ, with ρ = - 1.4. For the series where Ar was varied, the data correlated much better with σ+, although ρ+ was only -0.6. This remarkably small effect of substituents in Ar constrasts with the effects seen in benzylic carbocations, but is consistent with the nitrilium structure, with most of the positive charge located on the nitrogen. Rate constant ratios kaz:kw, including the N-alkylnitrilium ion 2, are constant at ~104, with values of kaz well below the diffusion limit, even for the most reactive nitrilium ions. This is very different behaviour from that of carbocations and arylnitrenium ions of similar lifetimes in water. For these cations the rate constants kaz would be at or at least approaching the diffusion limit.
- Ruane, Patrick H.,Ahmed, Abid R.,McClelland, Robert A.
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p. 312 - 317
(2007/10/03)
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- Synthesis and basicity of 4-amino-2-phenylquinazolines
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A new group of 6-and 7-substituted compounds of 4-amino-2-phenylquinazoline were synthesized by reaction of N-arylbenzimidoyl chlorides with cyanamide in the presence of TiCl4. The products were identified by spectroscopic methods, their dissoc
- Zielinski, Wojciech,Kudelko, Agnieszka
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p. 895 - 899
(2007/10/03)
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- Preparation of 1,5-disubstituted tetrazoles under phase-transfer conditions
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Imidoyl chlorides, obtained by common methods from a wide range of aromatic mono- and diamides, are smoothly converted to the corresponding tetrazoles in high yields by treatment with NaN3 under phase-transfer conditions.
- Artamonova,Zhivich,Dubinskii,Koldobskii
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p. 1428 - 1430
(2007/10/03)
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- Non-steroidal anti-inflammatory agents, Part 19. E-2-pyrrolizin-5-yl acrylic acids as potent dual or selective inhibitors of bovine cyclooxygenase and 5-lipoxygenase.
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The pyrrolizinyl substituted acrylic acid derivatives represent another class of dual and selective inhibitors of cyclooxygenase and 5-lipoxygenase. By modifying their substitution pattern at the phenyl moiety of C-6 the balance between the activity again
- Dannhardt,Kiefer,Nowe
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p. 681 - 686
(2007/10/03)
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- Synthesis of 4-Aminoquinazoline Derivatives
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The reaction of N-phenylimidoyl chlorides (2) with cyanamide and N,N-dimethylcyanamide (4) was studied.At the first stage, linear products like 1-amino-1-chloro-3,5-diphenyl-2,4-diaza-1,3-butadienes (6) were obtained.They underwent cyclization to 4-aminoq
- Zielinski, W.,Mazik, M.
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p. 489 - 498
(2007/10/02)
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- REACTIONS OF IMIDIC ACID DERIVATIVES WITH NUCLEOPHILIC REAGENTS. THE EFFECT OF WATER ON THE AMINOLYSIS RATE OF IMIDOYL CHLORIDES IN ORGANIC MEDIA. MECHANISMS IN THE "BOUNDARY" REGIONS
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The effect of water (as a catalyst) on the rate of the reaction of N-arylbenzimidoyl chlorides C6H5CCl=NC6H4R with 4-dimethylaminopyridine in acetonitrile, propylene carbonate, γ-butyrolactone, benzonitrile, methylene chloride, dioxane (R = 4-Cl), and ace
- Saveelova, V. A.,Taran, N. A.,Drizhd, L. P.
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p. 2020 - 2030
(2007/10/02)
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- PYRAZOLO(1,5-c)PYRIMIDINES FROM PYRYLIUM SALTS AND AMIDRAZONES AND PYRIDINE IMIDOYL-N-IMIDES FROM IMIDOYL CHLORIDES
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2,4,6-Triphenylpyrylium salts react with unsubstituted amidrazones to give dihydropyrazolo(1,5-c)pyrimidines or salts of pyridine imidoyl-N-imides.Pyridine imidoyl-N-imides are conveniently prepared from N-aminopyridinium and imidoyl chlorides.
- Katritzky, Alan R.,Tomas, Alberto Tarraga
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- Studies of N-Acyl-2-pyridinecarboxanilides. Preparation by Various Reactions Sequences and Reaction with Hydrogen Chloride to give Acyl Imidate Hydrochlorides through an Intramolecular N -> O Acyl Migration
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The preparation of N-acyl-2-pyridinecarboxanilides from imidoyl chlorides and salts of carboxylic acids is reported.Only small amounts of the same N-acylimides are obtained from acylations of 2-pyridinecarboxanilides with acyl chlorides and a base.Treatme
- Moerkved, Eva H.
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p. 313 - 318
(2007/10/02)
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