Chemistry of polyhalogenated nitrobutadienes, 17: Efficient synthesis of persubstituted chloroquinolinyl-1H-pyrazoles and evaluation of their antimalarial, anti-SARS-CoV-2, antibacterial, and cytotoxic activities

• Viktor A. Zapol’skii,
• Isabell Berneburg,
• Ursula Bilitewski,
• Melissa Dillenberger,
• Katja Becker,
• Stefan Jungwirth,
• Aditya Shekhar,
• Bastian Krueger and
• Dieter E. Kaufmann

Beilstein J. Org. Chem. 2022, 18, 524–532, doi:10.3762/bjoc.18.54

• -nitro-1H-pyrazoles bearing a dichloromethyl and an amino or thio moiety at C3 and C5 has been prepared in yields up to 72% from the reaction of 1,1-bisazolyl-, 1-azolyl-1-amino-, and 1-thioperchloro-2-nitrobuta-1,3-dienes with 7-chloro-4-hydrazinylquinoline. A new way for the formation of a pyrazole

• ± 0.04 µM (100 ng/mL, 200 nM), respectively. Two compounds (3b and 10d) have also been tested for anti-SARS-CoV-2, antibacterial, and cytotoxic activity. Keywords: antimalarial activity; anti-SARS-CoV-2 activity; chloroquine; 2-nitroperchlorobutadiene; nucleophilic vinylic substitution; 1H-pyrazoles

• precursors for a diverse variety of synthetically and/or physiologically interesting chemical compounds. Recently, we have developed an efficient method for the synthesis of persubstituted nitropyrazoles from diene 1 [14]. In this paper we are describing the formation of uniquely persubstituted 1H-pyrazoles

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

Synthesis of 2H-furo[2,3-c]pyrazole ring systems through silver(I) ion-mediated ring-closure reaction

• Vaida Milišiūnaitė,
• Rūta Paulavičiūtė,
• Eglė Arbačiauskienė,
• Vytas Martynaitis,
• Wolfgang Holzer and
• Algirdas Šačkus

Beilstein J. Org. Chem. 2019, 15, 679–684, doi:10.3762/bjoc.15.62

• and efficient procedure to access the 2H-furo[2,3-c]pyrazole ring system was developed by employing the silver(I) ion-mediated ring-closure reaction of 4-alkynyl-3-hydroxy-1-phenyl-1H-pyrazoles as a key step. The required intermediate hydroxyalkynyl substrates for this reaction were prepared by a Pd

• cyclization of readily available 4-alkynyl-3-hydroxy-1H-pyrazoles can be used as an efficient method to access many novel 2,5-disubstituted 2H-furo[2,3-c]pyrazoles. Keywords: 5-endo-dig cyclization; 2H-furo[2,3-c]pyrazole; pyrazole; silver(I) catalyst; Sonogashira coupling; Introduction Heterocyclic ring

• -furo[2,3-c]pyrazoles starting from commercially available 1-phenylpyrazol-3-ol. Iodination of the latter compound with iodine in DMF smoothly afforded 1-phenyl-4-iodopyrazol-3-ol, which can undergo a Pd-catalyzed coupling with terminal alkynes to give the corresponding 4-alkynyl-3-hydroxy-1-phenyl-1H

Molecular iodine-catalyzed one-pot multicomponent synthesis of 5-amino-4-(arylselanyl)-1H-pyrazoles

• Camila S. Pires,
• Daniela H. de Oliveira,
• Maria R. B. Pontel,
• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Diego Alves,
• Raquel G. Jacob and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2018, 14, 2789–2798, doi:10.3762/bjoc.14.256

• de Santa Maria – UFSM, 97105-900, Santa Maria, RS, Brazil 10.3762/bjoc.14.256 Abstract A one-pot iodine-catalyzed multicomponent reaction has been developed for the selective preparation of 5-amino-4-(arylselanyl)-1H-pyrazoles from a diverse array of benzoylacetonitriles, arylhydrazines and diaryl

• imidazopyridines, for example, is widely found in literature [6][7]. However, the preparation of 4-arylselanyl-1H-pyrazoles is quite scarce. Tiecco and co-workers described the preparation of phenylseleno substituted pyrazolidines by reacting allylhydrazines with phenylselanenyl sulfate generated in situ (Scheme 1

• the 3-methyl-5-methylsulfanyl-4-phenylselanyl-1H-pyrazole [10]. Our research group described the multicomponent synthesis of 3,5-dimethyl-4-arylselanyl-1H-pyrazoles catalyzed by copper iodide using DMSO as solvent [4]. More recently, Zora and co-workers reported the one-pot preparation of 4

Chemistry of polyhalogenated nitrobutadienes, 14: Efficient synthesis of functionalized (Z)-2-allylidenethiazolidin-4-ones

• Viktor A. Zapol’skii,
• Jan C. Namyslo,
• Mimoza Gjikaj and
• Dieter E. Kaufmann

Beilstein J. Org. Chem. 2014, 10, 1638–1644, doi:10.3762/bjoc.10.170

• cyclization step, a series of (Z)-2-allylidenethiazolidin-4-ones was obtained in yields up to 81%. Some subsequent reactions have been examined too, such as the formation of perfunctionalized 1H-pyrazoles upon treatment with hydrazine. Thiazolidinones are as well known for their physiological activities as

• for their application in optoelectronics. Keywords: atropisomers; cyclization; 2-nitroperchlorobutadiene; 1H-pyrazoles; thiazolidin-4-ones; Introduction Preliminary studies in the field of polyhalogenated nitrobutadienes have already shown the enormous potential of pentachloro-2-nitro-1,3-butadiene

• ). Formation of thiazolidin-4-ones 7–19. Assumed mechanism for the formation of thiazolidin-4-ones 7–18. Substitution reactions of the precursors 3 and 5 with additional amines. Synthesis of 5-arylmethylidenethiazolidin-4-ones 22–26 and 1H-pyrazoles 27, 28. Assumed mechanism for the formation of 1H-pyrazole 27

Efficient synthesis of 1,3-diaryl-4-halo-1H-pyrazoles from 3-arylsydnones and 2-aryl-1,1-dihalo-1-alkenes

• Yiwen Yang,
• Chunxiang Kuang,
• Hui Jin,
• Qing Yang and
• Zhongkui Zhang

Beilstein J. Org. Chem. 2011, 7, 1656–1662, doi:10.3762/bjoc.7.195

• , Fudan University, Handan Road 220, Shanghai 200433, China 10.3762/bjoc.7.195 Abstract An efficient synthesis of 1,3-diaryl-4-halo-1H-pyrazoles was achieved. The synthesis involves the [3 + 2] dipolar cycloaddition of 3-arylsydnones and 2-aryl-1,1-dihalo-1-alkenes. The process proceeds smoothly in

• moderate to excellent yields. 1,3-Diaryl-4-halo-1H-pyrazoles are found to be important intermediates that can easily be converted into 1,2,5-triaryl-substituted pyrazoles via Pd-catalyzed C–H bond activation. Keywords: C–H bond activation; cycloaddition; dihaloalkenes; pyrazole; sydnones; Introduction

• unknown, as is the direct formation of 4-halopyrazoles through the [3 + 2] dipolar cycloaddition of sydnones. In the present study, a convenient and efficient synthesis of a series of new 1,3-diaryl-4-halo-1H-pyrazoles 3 in moderate to excellent yields is reported. The route employed involves 1,3-dipolar

Approaches towards the synthesis of 5-aminopyrazoles

• Ranjana Aggarwal,
• Vinod Kumar,
• Rajiv Kumar and
• Shiv P. Singh

Beilstein J. Org. Chem. 2011, 7, 179–197, doi:10.3762/bjoc.7.25

• or 34) on Merrifield resin in the first step. Reaction of the resin-bound sulfonyl intermediate 31 with hydrazine, followed by release from the resin and intramolecular cyclization, afforded 4-arylsulfonyl-3,5-diamino-1H-pyrazoles 32. Reaction of the resin-bound carbonyl intermediate 35 with

• hydrate afforded 5-amino-3-(pyrrol-2-yl)pyrazole-4-carbonitrile (50) (Scheme 12) [43]. Synthesis of 5-amino-3-aryl-1H-pyrazoles 53 has been reported using benzoylacetonitrile 51 as starting material. Substituted phenylhydrazines on reaction with substituted 1-aminocinnamonitriles 52, obtained from base

• catalyzed reaction of benzoylacetonitrile 51 and acetonitrile, yielded 5-amino-3-aryl-1H-pyrazoles 53. Corresponding amide derivatives, i.e., N-(1,3-diaryl-1H-pyrazol-5-yl)benzamides 54 were prepared by further treating aminopyrazoles 53 with substituted benzoyl chlorides in DCM (Scheme 13) [44]. 3