Synthesis of pyrano[3,2-c]quinolones and furo[3,2-c]quinolones via acid-catalyzed tandem reaction of 4-hydroxy-1-methylquinolin-2(1H)-one and propargylic alcohols

Two acid-catalyzed tandem reactions between 4-hydroxy-1-methylquinolin-2(1H)-one and propargylic alcohols are described. Depending mainly on the propargylic alcohol used, these tandem reactions proceed via either a Friedel–Crafts-type allenylation followed by 6-endo-dig cyclization sequence to form pyrano[3,2-c]quinolones or a Friedel–Crafts-type alkylation and 5-exo-dig ring closure sequence to afford furo[3,2-c]quinolones in moderate-to-high yields. The pyrano[3,2-c]quinolones products could be further transformed to tetracyclic 4,9-dihydro-5H-cyclopenta[lmn]phenanthridin-5-one derivatives.

Two acid-catalyzed tandem reactions between 4-hydroxy-1-methylquinolin-2(1H)-one and propargylic alcohols are described.     

Rh(iii)-catalyzed spiroannulation of 3-arylquinoxalin-2(1H)-ones with alkynes: practical access to spiroquinoxalinones

The Rh(iii)-catalyzed synthesis of spiroquinoxalinone derivatives from 3-arylquinoxalin-2(1H)-ones and alkynes via a C–H functionalization/[3 + 2] annulation sequence has been developed. This method, featuring low catalyst loading, was amenable to Gram scale synthesis and tolerated a variety of functional groups and substitution patterns on the aryl rings, providing the target products in good to excellent yields.

The use of imines as a H acceptor for Rh(iii)-catalyzed spirocyclization of 3-arylquinoxalinones and alkynes via a C–H functionalization/[3 + 2] annulation sequence has been achieved.     

Rhodium(iii)-catalyzed C–H annulation of 2-acetyl-1-arylhydrazines with sulfoxonium ylides: synthesis of 2-arylindoles

An efficient Rh(iii)-catalyzed synthesis of 2-arylindole derivatives via intermolecular C–H annulation of arylhydrazines with sulfoxonium ylides was accomplished. A variety of 2-acetyl-1-arylhydrazines with sulfoxonium ylides were converted into 2-arylindoles in satisfactory yields. Excellent selectivity and good functional group tolerance of this transformation were also observed.

Rh(iii)-catalyzed intermolecular C–H annulation of arylhydrazines with sulfoxonium ylides for synthesis of 2-arylindole derivatives was well established.     

Photoinitiated decarboxylative C3-difluoroarylmethylation of quinoxalin-2(1H)-ones with potassium 2,2-difluoro-2-arylacetates in water

An efficient and green strategy for the preparation of C3-difluoroarylmethylated quinoxalin-2(1H)-one via a visible-light-induced decarboxylative C3-difluoroarylmethylation of quinoxalin-2(1H)-one with potassium 2,2-difluoro-2-arylacetate in water at room temperature was developed. This photoinduced reaction generated the desired products in good yields under simple and mild conditions.

An efficient visible-light-induced decarboxylative C3-difluoroarylmethylation of quinoxalin-2(1H)-one with potassium 2,2-difluoro-2-arylacetate in water at room temperature was developed.     

One-pot construction of diverse and functionalized isochromenoquinolinediones by Rh(iii)-catalyzed annulation of unprotected arylamides with 3-diazoquinolinediones and their application for fluorescence sensor

A facile and efficient Rh(iii)-catalyzed annulation of arylamides with 3-diazoquinolinediones for the construction of diverse and highly functionalized isochromenoquinolinediones is described. Furthermore, the methodology is applicable for delivering various relevant molecules such as pyridopyranoquinolindiones, thienopyranoquinolinones, and indolopyranoquinolinone. The reaction proceeds via cascade C–H activation, carbene insertion, and intramolecular lactonization. The reaction exhibits high atom economy, good functional group tolerance, and high regioselectivity. The synthesized compound can also behave as a potent fluorescence sensor for Fe³⁺ ion.

An efficient Rh(iii)-catalyzed annulation of arylamides with 3-diazoquinolinediones for the construction of diverse and highly functionalized isochromenoquinolinedione derivatives is described.     

Urazolium diacetate as a new,efficient and reusable Brønsted acid ionic liquid for the synthesis of novel derivatives of thiazolidine-4-ones

Urazolium diacetate catalyzed synthesis of new derivatives of 1,3-thiazolidine-4-ones (azo dispersive dyes family) via multicomponent reaction of various aldehydes, thioglycolic acid and 4-aminoazobenzene under solvent-free reaction was reported. This avenue for the synthesis of new derivatives of thiazolidine-4-one has advantages as: short reaction times, high yields, green aspect of chemistry and environmental friendliness, easy workup, solvent-free conditions and convenient operation.

Urazolium diacetate catalyzed synthesis of new derivatives of 1,3-thiazolidine-4-ones (azo dispersive dyes family) via multicomponent reaction of various aldehydes, thioglycolic acid and 4-aminoazobenzene under solvent-free reaction was reported.     

An efficient synthesis of 4-phenoxy-quinazoline, 2-phenoxy-quinoxaline,and 2-phenoxy-pyridine derivatives using aryne chemistry

Herein we report the mild and efficient synthesis of 4-phenoxyquinazoline, 2-phenoxyquinoxaline, and 2-phenoxypyridine derivatives from the starting materials viz. quinazolin-4(3H)-one, quinoxalin-2(1H)-one, and pyridin-2(1H)-one and aryne generated in situ from 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and cesium fluoride. This synthetic methodology gives a new environmentally benign way for the preparation of several unnatural series of 4-phenoxyquinazoline, 2-phenoxyquinoxaline and 2-phenoxypyridine compounds with high yields and broad substrate scope.

Efficient synthesis of 4-phenoxyquinazoline, 2-phenoxyquinoxaline, 2-phenoxypyridine derivatives were generated of aryne from 2-(trimethylsilyl)phenyltrifluoromethanesulfonate with cesium fluoride.     

Mg3N2-assisted one-pot synthesis of 1,3-disubstituted imidazo[1,5-a]pyridine

A novel Mg₃N₂-assisted one-pot annulation strategy has been developed via cyclo-condensation reaction of 2-pyridyl ketones with alkyl glyoxylates or aldehydes, allowing the formation of imidazo[1,5-a]pyridines exclusively with an exellent yield.

A novel Mg₃N₂-assisted one-pot annulation strategy has been developed via cyclo-condensation reaction of 2-pyridyl ketones with alkyl glyoxylates or aldehydes, allowing the formation of imidazo[1,5-a]pyridines exclusively with an exellent yield.     

Preparation of 3,5-diarylsubstituted 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones via base-assisted cyclization of 3-cyanoketones

A convenient preparative method is developed allowing for expeditious assembly of 3,5-diarylsubstituted 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones from routinely available inexpensive synthetic precursors. These compounds could not be prepared via the previously known protocols, as 2-aminofuran derivatives were produced instead.

The highly efficient oxidative cyclization of 1,3-diarylsubstituted 3-cyanoketones yielded 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones.     

A facile approach to 2-alkoxyindolin-3-one and its application to the synthesis of N-benzyl matemone

2-Alkoxycarbonylindolin-3-one is synthesized from a methoxyglycine derivative via a 1,2-aza-Brook rearrangement followed by cyclization with bis(trimethylsilyl)aluminum chloride. A short-step synthesis of N-benzyl matemone is successfully carried out using the present indolin-3-one synthesis.

A short-step synthesis of N-benzyl matemone has been successfully carried out using a newly discovered 2-ethoxycarbonylindolin-3-one synthesis.     

K3PO4-promoted domino reactions: diastereoselective synthesis of trans-2,3-dihydrobenzofurans from salicyl N-tert-butanesulfinyl imines and sulfur ylides

An efficient domino annulation between sulfur ylides and salicyl N-tert-butylsulfinyl imines was developed. The reaction proceeds with a diastereodivergent process, the configuration of the sulfinyl group determining the stereochemical course of the reaction. The method allows the synthesis of a highly substituted trans-2,3-dihydrobenzofuran skeleton with high yield and good chemo- and diastereoselectivity.

The diastereospecific formation of trans-2,3-dihydrobenzofurans has been achieved via a domino annulation between sulfur ylides and salicyl N-tert-butylsulfinyl imines with a diastereodivergent process.     

Rh(iii)-catalyzed synthesis of tetracyclic isoquinolinium salts via C–H activation and [4+2] annulation of 1-phenyl-3,4-dihydroisoquinolines and alkynes in ethanol

An efficient and convenient method to construct tetracyclic isoquinolinium salts via [Cp*RhCl₂]₂ catalyzed C–H activation and [4 + 2] annulation reactions in ethanol is described. This reaction is very fast and highly efficient in the green solvent ethanol. The reaction works with a broad substrate scope affording the products in good to excellent yields in a short time. Moreover, a ratio of S/C up to 10 000 could be achieved with gram scale synthesis.

An efficient method to construct tetracyclic isoquinolinium salts via C–H activation and [4 + 2] annulation reactions in ethanol is described.     

Synthesis,anti-mycobacterial and cytotoxic evaluation of substituted isoindoline-1,3-dione-4-aminoquinolines coupled via alkyl/amide linkers

A series of secondary amine-substituted isoindoline-1,3-dione-4-aminoquinolines were prepared via microwave heating and assayed for their anti-mycobacterial activities. The compound with a butyl chain as a spacer between the two pharmacophores and piperidine as the secondary amine component on the isoindoline ring was the most potent and non-cytotoxic among the synthesized compounds, exhibiting a minimum inhibitory concentration (MIC₉₉) of 6.25 μg mL⁻¹ against Mycobacterium tuberculosis.

A series of secondary amine-substituted isoindoline-1,3-dione-4-aminoquinolines were prepared via microwave heating and assayed for their anti-mycobacterial activities.     

Synthesis of tetrahydro-β-carbolines from 2-indolylmethyl azides and propargylic alcohols

A facile and efficient route to tetrahydro-β-carbolines from 2-indolylmethyl azides and propargylic alcohols via acid-catalyzed dehydrative annulation reactions is described. This reaction proceeds through a cascade sequence of Friedel–Crafts-type alkylation followed by intramolecular “Click” reaction, involving the formation of multiple chemical bonds in a single operation with excellent atom-economy and broad functional group tolerance.

The synthesis of tetrahydro-β-carbolines from 2-indolylmethyl azides and propargylic alcohols via acid-catalyzed dehydrative [4 + 2]-annulation reaction is described.     

Efficient and stereoselective one-pot synthesis of benzo[b]oxazolo[3,4-d][1,4]oxazin-1-ones

An efficient and mild one-pot convergent synthesis protocol has been developed for benzo[b]oxazolo[3,4-d][1,4]oxazin-1-one derivatives through the Mitsunobu reaction and sequential cyclization. Various tricyclic fused benzoxazinyl-oxazolidinones (20 examples) were obtained in good to excellent yields and high enantioselectivities with facile operation. Furthermore, four stereoisomers were afforded respectively in high ee values (>97.8%) via using different chiral 2,3-epoxy-4-trityloxybutanol. This methodology has been applied to the synthesis of key intermediates of drug candidates.

An efficient and mild one-pot convergent synthesis protocol has been developed for benzo[b]oxazolo[3,4-d][1,4]oxazin-1-one derivatives through the Mitsunobu reaction and sequential cyclization.     

Rapid synthesis of 3-amino-1H-isochromene from ortho-ynamidyl het(aryl) aldehyde derivatives

A simple and original efficient synthesis of 3-amino-1H-isochromene bearing a bromine atom at the C-1 position via a 6-endo-cyclization approach from in situ generated ortho-ynamidyl het(aryl) aldehyde derivatives is achieved under mild reaction conditions and with good yields. Original ortho-ynamidyl benzaldehyde compounds were also successfully obtained.

Fast synthesis of 3-amino-1H-isochromene from in situ generated ortho-ynamidyl het(aryl) aldehyde derivatives.     

A novel superparamagnetic powerful guanidine-functionalized γ-Fe2O3 based sulfonic acid recyclable and efficient heterogeneous catalyst for microwave-assisted rapid synthesis of quinazolin-4(3H)-one derivatives in Green media

The novel organic–inorganic nanohybrid superparamagnetic (γ-Fe₂O₃@CPTMS–guanidine@SO₃H) nanocatalyst modified with sulfonic acid represents an efficient and green catalyst for the one-pot synthesis of quinazolin-4(3H)-one derivatives via three-component condensation reaction between anthranilic acid, acetic anhydride and different amines under microwave irradiation and solvent-free conditions (4a–q). XRD, FT-IR, FE-SEM, TGA, VSM and EDX were used to characterize this new magnetic organocatalyst. Outstanding performance, short response time (15–30 min), simple operation, easy work-up procedure, and avoidance of toxic catalysts can be regarded as its significant advantages. Moreover, it can be easily separated from the reaction solution through magnetic decantation using an external magnet, and recycled at least six times without notable reduction in its activity.

A novel organic–inorganic nanohybrid superparamagnetic nanocatalyst (γ-Fe₂O₃@CPTMS–guanidine@SO₃H) represents an efficient and green catalyst for the one-pot synthesis of quinazolin-4(3H)-one derivatives via a three-component condensation reaction.     

Tin(iv) chloride mediated (3 + 2) annulation of trans-2-aroyl-3-styrylcyclopropane-1,1-dicarboxylates with nitriles: diastereoselective access to 5-vinyl-1-pyrroline derivatives

A tin(iv) chloride promoted (3 + 2) annulation of trans-2-aroyl-3-styrylcyclopropane-1,1-dicarboxylates with nitriles is reported. The transformation involves the Lewis acid assisted formation of 1,5-dipolar intermediates from the cyclopropane dicarboxylates and nitriles followed by cyclization. The reactions proceed in a highly diastereoselective manner and afford 5-vinyl-1-pyrroline derivatives in 60–88% yields.

A (3 + 2) annulation of trans-2-aroyl-3-styrylcyclopropane-1,1-dicarboxylates with nitriles is reported for the diastereoselective synthesis of 5-vinyl-1-pyrroline derivatives in 60–88% yields.     

CuI nanoparticle-catalyzed synthesis of tetracyclic benzo[e]benzo[4,5]imidazo[1,2-c][1,3]thiazin-6-imine heterocycles by SNAr-type C–S,C–N bond formation from isothiocyanatobenzenes and benzimidazoles

In this paper, a simple and practical synthesis of benzo[e]benzo[4,5]imidazo[1,2-c][1,3]thiazin-6-imine tetracyclic heterocycles via a CuI nanoparticle-catalyzed intramolecular C(sp²)–S coupling reaction is presented. This strategy provides a straightforward method for synthesizing analogs of the anti-HIV drug 3,4-dihydro-2H,6H-pyrimido[1,2-c][1,3]benzothiazin-6-imine (PD 404182). The reaction rate and yield were increased by employing CuI nanoparticles.

We proposed a practical synthesis of analogs of the anti-HIV drug 3,4-dihydro-2H,6H-pyrimido[1,2-c][1,3]benzothiazin-6-imine via a CuI nanoparticle-catalyzed intramolecular C(sp²)–S coupling reaction.     

Visible light enabled [4+2] annulation reactions for anthracenone-furans from 2,3-dibromonaphthoquinone and phenylbenzofurans

A facile visible light promoted approach to anthracenone-furans from readily available 2,3-dibromonaphthoquinones and phenylbenzofurans via a formal Diels Alder reaction is reported. This reaction involves wavelength-selective agitation of 4CzIPN, energy transfer to quinones, recombination of 1,6-biradicals and elimination to give anthracenone-furans in good to excellent yields in one pot.

A facile visible light promoted [4 + 2] annulation reaction from readily available starting materials using an organo-photocatalyst gave anthracenone-furans with up to 95% yield in one-pot.