Synthesis of azepino[1,2-<Emphasis Type="Italic">a</Emphasis>]benzimidazoles and imidazo[1,2-<Emphasis Type="Italic">a</Emphasis>]azepines

Fusion of 4-bromo-1,3-diphenyl-2-buten-1-ones (γ-bromodypnones) with 1,2-dimethyl-1H-benzimidazole and further treatment of the reaction product with a base (morpholine) gives 7,9-diaryl-5-methyl5,10-dihydroazepino[1,2-a]benzimidazol-11-ium bromides. The reaction of γ-bromodypnone with 1-alkyl-2-methyl-1H-imidazoles in benzene at 25 °C gives quaternary azolium salts. Upon heating their solutions in alcohol in the presence of K₂CO₃ the latter cyclize to 1-R-6,8-diaryl-1,5-dihydroimidazo[1,2-a]azepin-4-ium bromides or 1-R-6,8-diaryl-1H-imidazo[1,2-a]azepines depending on the nature of the substituent in the benzene rings and the substituent at the N(1) atom of the imidazole.     

Conjugate additions of carbon nucleophiles to cyclopentadienones

[reaction: see text] Reactions of cyclopentadienones 1 with alkylmagnesium bromides were investigated and gave 1,4 adduct and/or 1,2 adduct.     

Palladium-catalyzed regioselective arylation of imidazo[1,2-a]pyrimidine

Imidazo[1,2-a]pyrimidine can be arylated at the 3-position with aryl bromides in the presence of base and a catalytic amount of palladium. This provides an efficient one-step synthesis of 3-arylimidazo[1,2-a]pyrimidines from the unsubstituted heterocycle. [reaction: see text]     

New method for the annelation of a pyridine ring on derivatives of imidazole and benzimidazole

The interaction of (Z)-1,3-diaryl-4-bromo-2-buten-1-ones with 1-substituted (benz)imidazoles in benzene gave (Z)-1-R-3-(2,4-diaryl-4-oxo-2-butenyl)-1H-imidazolium bromides and (Z)-1-R-3-(2,4-diaryl-4-oxo-2-butenyl)-1H-benzimidazolium bromides which readily cyclize in the presence of base to form derivatives of 7,9-diarylpyrido[1,2-a]benzimidazole and 6,8-diarylpyrimidazo[1,2-a]pyridine. The effects of the nature of substituents in the benzene ring of the diarylbutenones and the substituent at N(1) in the (benz)imidazoles on the alkylation and cyclization reactions has been studied. The optimum conditions for the synthesis of the 5-R-4-hydroxy-2,4-diphenyl-4,5-dihydro-1H-pyrido[1,2-a]benz-imidazol-10-ium, 5-R-2,4-diaryl-4-hydroxy-4,5-dihydro-3H-pyrido[1,2-a]benzimidazol-10-ium, and 5-R-2,4-diaryl-5H-pyrido[1,2-a]benzimidazol-10-ium have been found.     

Oxidative bromination of imidazoheterocycle bromohydrates*

The behavior of imidazo[1,2-a]pyridinium, imidazo[1,2-a]pyrimidinium, and imidazo[2,1-b]thiazolium bromides derivatives in oxidative bromination reactions has been studied. It has been established that reaction products structures and their yields depend on the properties of the substituents in the bicycle and the oxidant concentration.     

Diastereoselective Synthesis of 1,10-Dihydropyrrolo [ 1,2-a] [1,10]phenanthroline Derivatives via 1,3-Dipolar Cycloaddition Reaction

The functionalized 1,10-dihydropyrrolo[1,2-a][1,10]phenanthroline derivatives were synthesized in good yields and with high diastereoselectivity by 1,3-dipolar cycloaddition reactions of N-phenacylphenanthrolinium bromides or N-ethoxycarbonylmethylene phenanthrolinium bromide with various nitrostyrenes in acetonitrile at room temperature in the presence of triethvlamine,     

One-pot synthesis of imidazo[1,2-b]pyrazole,imidazo[1,2-b]-1,2,4-triazole,imidazo[1,2-a]pyridine,imidazo[1,2-a]pyrimidine,imidazo[1,2-a]benzimidazole,and 1,2,4-triazolo[4,3-a]benzimidazole derivatives

Hydrazonoyl bromides 1a-c react with 5-amino-3-phenyl-1H-pyrazole, 5-amino-1H-1,2,4-triazole, 2-aminopyridine, and 2-aminobenzimidazole to afford the corresponding imidazol[1,2-b]pyrazoles 10, imidazo[1,2-b]-1,2,4-triazoles 11, imidazo[1,2-a]pyridines 16, imidazo[1,2-a]pyrimidines 17, and imidazo[1,2-a]benzimidazoles 20, respectively. Compounds 1a-c reacted also with 2-methylthiobenzimidazole to give 1,2,4-triazolo[4,3-a]benzimidazole derivatives 21. © 1997 John Wiley & Sons, Inc.     

Direct arylation of imidazo[1,2-a]pyridine at C-3 with aryl iodides, bromides, and triflates via copper(I)-catalyzed C-H bond functionalization

A convenient method for the copper(I)-catalyzed arylation of substituted imidazo[1,2-a]pyridine has been developed. This method is applicable to a variety of aryl electrophiles, including bromides, iodides, and triflates. It represents the first general process for C-3 arylation of substituted imidazo[1,2-a]pyridine by Cu(I) catalysis to construct various functionalized imidazo[1,2-a]pyridine core π-systems.     

Visible‐Light‐Promoted Generation of α‐Ketoradicals from Vinyl‐bromides and Molecular Oxygen: Synthesis of Indenones and Dihydroindeno[1,2‐c]chromenes

Ortho‐alkynylated α‐bromocinnamates can be converted by a visible‐light‐mediated photocascade reaction with molecular oxygen into either indenones or dihydroindeno[1,2‐c]chromenes. The one‐step process features key photochemical steps, that is, the initial activation of vinyl bromides through energy transfer to give α‐ketoradicals in a reaction with molecular oxygen, followed by α‐oxidation of an arene moiety by 6‐π electrocyclization, and subsequent hydroxylation by an electron‐transfer process from the same photocatalyst leads to the dihydroindeno[1,2‐c]chromenes.     

The formation of the indolizino[1,2-c]quinolinium system by a novel nucleophilic reaction

2-Methyl-3-(2-pyridyl)quinoline (1) with a bromomethyl ketone or ethyl bromoacetate yields 6-methyl-12-acylindolizino[1,2-c]quinolinium bromides ( 5–9 ). The acyl derivatives can be deacylated in acid yielding 6-methyl indolizino[1,2-c]quinolinium salts ( 4 ). Benzoylation of 4 yields the 12-benzoyl derivative ( 6 ). The deacylation product ( 4 ) has been synthesized from 2-acetamidophenacyl bromide ( 10 ) and 2-pyridylacetone ( 12 ).     

Condensed isoquinolines. 36*. Cyclization of N-alkyl-3-(2-benzoylbenzyl)azolium salts. A novel method of preparing azolo[<Emphasis Type="Italic">b</Emphasis>]isoquinolines

A novel method is proposed for the preparation of azolo[b]isoquinolines based on the alkylation of N-alkyl-1,3-diazoles or 1,3-thiazole derivatives using [2-(bromomethyl)phenyl](phenyl)methanone with subsequent cyclization of the quaternary azolium salts in the presence of base. The 10(11)-hydroxy derivatives of the 5,10-dihydro-1H-imidazo[1,2-b]isoquinolinium, 6,11-dihydro-5H-benzimidazo-[1,2-b]isoquinolinium, 5,10-dihydro-1H-[1, 2, 4]triazolo[4,3-b]isoquinolinium, or 5,10-dihydro[1, 3]-thiazolo[3,2-b]isoquinolinium bromides obtained in this way readily lose a molecule of water upon heating with HBr or Ac₂O to give the corresponding quasi-aromatic azolo[b]isoquinolinium salts.     

Copper(II)-catalyzed synthesis of benzo[f]pyrido[1,2-a]indole-6,11-dione derivatives via naphthoquinone difunctionalization reaction

Benzo[f]pyrido[1,2-a]indole-6,11-diones have been synthesized in high yields by copper(II)-catalyzed three-component reactions of acyl bromide, 1,4-naphthoquinone, and pyridine (or isoquinoline) via sp(2)-C-H difunctionalization of naphthoquinone followed by intramolecular cyclization and oxidative aromatization. In an attempt to expand the reaction scope and to help clarify the reaction mechanism, 1,3-dicarbonyl compounds are used in place of acyl bromides to take part in this reaction, and the benzo[f]pyrido[1,2-a]indole-6,11-diones derivatives are also obtained in excellent yields.     

Palladium-Catalyzed C-H Bond Functionalization of Benzo[1,2-b : 4,5-b′]dithiophene-4,8-dione: A One Step Access to 2-Arylbenzo[1,2-b : 4,5-b′]dithiophene-4,8-diones

The reactivity of benzo[1,2-b : 4,5-b′]dithiophene-4,8-dione in Pd-catalyzed C−H arylation was investigated. Using aryl bromides as aryl source in the presence of carbonate bases in 1,4-dioxane, the mono-C2-arylated benzo[1,2-b : 4,5-b′]dithiophene-4,8-diones were regioselectively obtained. This procedure allowed to introduce both electron-rich and electron-poor aryl substituents on the benzo[1,2-b : 4,5-b′]dithiophene-4,8-dione unit. These conditions were also effective for the coupling with 1-bromonaphthalene, 9-bromophenanthrene as well as aryl bromides bearing synthetically useful nitrile, chloro and methoxy substituents. The photophysical properties of representative arylated compounds have been performed by joint experimental and theoretical studies.     

Trinuclear Gold-Catalyzed 1,2-Difunctionalization of Alkenes

Activated alkyl halides have been extensively explored to generate alkyl radicals with Ru- and Ir- photocatalysts for 1,2-difunctionalization of alkenes, but unactivated alkyl bromides remain challenging substrates due to their strong reduction potential. Here we report a three-component 1,2-difunctionalization reaction of alkenes, unactivated alkyl bromides and nucleophiles (e.g., amines and indoles) using a trinuclear gold catalyst [Au₃(tppm)₂](OTf)₃. It can achieve the 1,2-aminoalkylation and 1,2-alkylarylation readily. This protocol has a broad reaction scope and excellent functional group compatibility (>100 examples with up to 96 % yield). It also affords a robust formal [2+2+1] cyclization strategy for the concise construction of pyrrolidine skeletons under mild reaction conditions. Mechanistic studies support an inner-sphere single electron transfer pathway for the successful cleavage of inert C−Br bonds.     

A facile and convenient synthesis of novel imidazo[1,2-b] isoxazoles and their Mannich bases as potential biodynamic agents

A series of novel imidazo[1,2-b]isoxazoles 3 and their Mannich bases 4–6 were synthesized via convenient reactions. The reaction of 3-aminoisoxazole 1 with substituted phenacyl bromides 2 in dry ethanol afforded the corresponding 6-methyl-3-aryl imidazo[1,2-b]isoxazoles 3 in good yields.Compounds 3 on treatment with 37% formaline and secondary amines furnished the corresponding novel Mannich bases viz., 6-methyl-3-aryl-2-(morpholine/pyrrolidin-1-yl/piperidin-1-yl)-methyl-imidazo[1,2-b]isoxazoles 4–6.     

4a-Alkyl Derivatives of 5-Oxo-4H-4a,5-dihydroindeno[1,2-b]pyridine

High selectivity has been discovered for the C-alkylation of ambident anions of 5-oxo-1H-4,5-dihydroindeno[1,2-b]pyridines with ethyl bromoacetate, allyl, propargyl, and phenacyl bromides, which leads to the formation of the corresponding 4a-substituted 5-oxo-4H-4a,5-dihydroindeno[1,2-b]pyridines in high yield.     

Synthesis of polysubstituted imidazo[1,2-a]pyridines via microwave-assisted one-pot cyclization/Suzuki coupling/palladium-catalyzed heteroarylation

A new and efficient method for the synthesis of 2,3,6-trisubstituted imidazo[1,2-a]pyridine derivatives using a microwave-assisted one-pot, two-step Suzuki/heteroarylation or one-pot, three-step cyclization/Suzuki/heteroarylation was developed. Polysubstituted compounds are obtained in good yield from 2-amino-5-halogenopyridines, 2-halogenocarbonyl derivatives, boronic acids, and heteroaryl bromides.     

Diversity-oriented decoration of pyrrolo[1,2-a]pyrazines

Diversity-oriented synthesis of a chemical library based on a pyrrolo[1,2-a]pyrazine core is described by using palladium-catalyzed direct C6 arylation of pyrrolo[1,2-a]pyrazines with various aryl bromides. The starting materials, pyrrolo[1,2-a]pyrazines, were easily synthesized by the base-mediated N-alkylation of pyrrole-2-carboxaldehyde with several 2-bromoacetophenones followed by dehydrative cyclization with incorporation of nitrogen by the action of ammonium acetate. Introduction of other functional groups on this chemical scaffold is also discussed herein.     

Palladium-catalyzed silylation of aryl bromides leading to functionalized aryldimethylsilanols

[reaction: see text] A mild and general palladium-catalyzed insertion of 1,2-diethoxy-1,1,2,2-tetramethyldisilane into a variety of aryl bromides affords the aryldimethylsilyl ethers in high yields. Hydrolysis of the ethers under pH-optimized conditions results in the exclusive formation of the desired aryldimethylsilanols.     

An Efficient Synthetic Protocol for Quinoxalinones,Benzoxazinones, and Benzothiazinones from 2‐Oxo‐2‐aryl‐acetyl Bromide Precursors

α‐Bromoketones undergo selenium dioxide oxidation to yield reactive 2‐oxo‐2‐arylacetyl bromides that are trapped by aryl‐1,2‐diamines, 1,2‐aminophenol or 1,2‐aminothiophenol to give quinoxalinones, benzoxazinones, and benzothiazinones, respectively, in good yield.