Formation of aromatic rings through enamine annulation

Condensation of pyrrolidine enamine of ketones with 1, 4-diacetoxy-2-butanone provides a new, concise synthetic route to substituted benzenes, dihydroindenes, tetrahydronaphthalenes, and di- and octahydrophenanthrenes. The reaction produced modest yields with regiocontrol of the secondary amine substituent.     

Nucleophilic reactivities of tributylstannyl-substituted furans and thiophenes

Kinetic investigations of the reactions of benzhydryl cations with stannylated furans and thiophenes suggest that 2-(tributylstannyl)furan and -thiophene are preferentially attacked at the 5-position (k(rel), FcPhCH(+), 20 degrees C, CH(2)Cl(2)).     

High-yield syntheses of 2,3-disubstituted furans and thiophenes

The course of lithiation of furan- and thiophene-2-carboxylic acids is critically dependent on the identity of the lithium base allowing high-yielding syntheses of 2,3- and 2,5-disubstituted thiophenes: the proposed use of a trimethylsilyl blocking group to control metallation in the furan acid provides a useful route to 2,3-disubstituted furans.     

Conformation of substituted five-membered rings

Proton magnetic resonance chemical shifts and coupling constants for some 5-substituted dihydrofurans, dihydrofuran and dihydrothiophene fused rings are reported, the substituents being methyl, ethyl and phenyl. The observed coupling constants are consistent with buckled rings, in which it appears that a conformation with pseudo-equatorial substituents is predominant.     

Pd-catalyzed olefination of furans and thiophenes with allyl esters

A direct Pd(II)-catalyzed olefination of furans and thiophenes with allyl esters is demonstrated. Under the typical conditions, the dehydrogenative Heck coupling reactions of heteroarenes with allylic esters proceeded via a β-H elimination rather than a β-OAc elimination to give the corresponding γ-substituted allylic esters.     

Synthesis and fluorescent properties of some new unsymmetricbis-benzothiazolyl furans and thiophenes

Summary Some newmono- andbis-benzothiazolyl compounds with furan or thiophene nuclei were synthesized by multistep reactions from the corresponding furan and thiophene aldehydes. The data obtained from emission spectra show a large influence of the benzothiazole rings on the relative quantum efficiency of the compounds under investigation.

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Synthese und Fluoreszenzeigenschaften von neuen unsymmetrischenbis-Benzothiazolylfuranen und thiophenen

Zusammenfassung Einige neuebis-Benzothiazolylverbindungen mit einem Furan- bzw. Thiophenenring wurden in einer mehrstufigen Reaktion dargestellt. Die Fluoreszenzdaten der untersuchten Verbindungen zeigen einen großen Einfluß der Benzothiazolringe auf die relative Fluoreszenzquantenausbeute.

     

Electrochemical polymerization of substituted thiophenes

The electrochemical polymerization of 3-(n-butyl)thiophene and of several 3- or 3,4- substituted α, α'-terthienyls is described and the properties of the conducting polymers are discussed. A solution in acetonitrile of the terthienyl substituted by a potassium propylsulfonate group is polymerizable as such, and the polymer is the first proven example of a self-doped conducting polymer. This polymer dissolves readily in water and remains partially self-doped in solution.     

Palladium-catalyzed alkenation of thiophenes and furans by regioselective C-H bond functionalization

A palladium-catalyzed direct alkenation of thiophenes and furans has been developed in the presence of AgOAc and pyridine. A variety of olefinic substrates such as acrylates, acrylamides, and acrylonitrile can perform the direct oxidative coupling reactions with various thiophenes and furans to give the mono-alkenylated products in good yields. In most cases, the (E)-isomers were isolated as the major products.     

Synthesis of multisubstituted furans, pyrroles, and thiophenes via ynolates

An efficient synthetic method for the preparation of multisubstituted furans, thiophenes, and pyrroles using ynolates was developed. This novel formal [4 + 1] annulation by C2-C3 and C3-C4 bond formations includes cycloaddition, cyclization, decarboxylation, and dehydration as key steps.     

A general approach to arylated furans,pyrroles, and thiophenes

A general and practical synthetic method for aryl-substituted five-membered heterocycles has been developed. In the presence of KOH (30%), 1,4-diaryl-1,3-butadiynes undergo the cyclocondensation reaction with water, primary amines, and Na₂S·9H₂O in DMSO at 80 °C to afford 2,5-diarylfurans, 1,2,5-trisubstituted pyrroles, and 2,5-diarylthiophenes in good to high yields. Further studies have disclosed that aryl-substituted five-membered heterocycles can be also synthesized by a one-pot, two-step strategy from the terminal alkynes in DMSO firstly catalyzed by CuCl, and then via addition of KOH to promote the cyclocondensation of 1,3-butadiynes generated in situ.     

Palladium-catalyzed direct oxidative vinylation of thiophenes and furans under weakly basic conditions

The palladium-catalyzed oxidative coupling of thiophenes and furans with alkenes proceeds in the presence of copper and lithium salts as oxidant and additive, respectively, under weakly basic or almost neutral conditions to afford the corresponding vinylated heteroarenes. Under such conditions, diphenyl(hydroxy)methyl and acetal functions on the heteroarene substrates are tolerable. The former function on a thiophene ring can be substituted by palladium-catalyzed arylation via C-C bond cleavage after the vinylation to produce 2-aryl-5-vinylthiophenes.     

Thia-acyliminium cyclisations : Synthesis of five-membered rings and macrocycles

Cyclisations of carbinollactams 1b–3b afford macrocycles 4–6 in good yield by the intermediacy of N-acyliminium species. A similar process applied to lactams 21b–25b affords the pyrrolizidine type compounds 26–35 through consecutive azonium-Cope rearrangement and N-acyliminium ring closure. Additional results are concerned with the use of aromatic rings as π-nucleophiles.     

Chromatographic and IR characteristics of methyl-, formyl-, and acetyl-substituted furans and thiophenes

The GC and FTIR spectral characteristics of methyl-, formyl-, and acetyl-substituted furans and thiophenes were determined. The substituent contributions to the retention indices were calculated. It was found that contributions of identical substituents differ according to the nature of the heterocycle, their position relative to the heteroatom and other neighboring groups. The contributions of CH₃-, CHO-, and COCH₃-groups in the -position of the cycle for monosubstituted substances were equal to the contributions of these groups in monosubstituted benzenes. The contributions of carbonyl groups in the-position were greater than in the -position for the same groups. The contributions were found to be nonadditive for disubstituted methyl and carbonyl-containing thiophenes and furans. The presence of two carbonyl groups as substituents in furans and thiophenes results in reduction of the sorption energy of the latter, which is known as «negative» -effect. The scheme fora priori calculation of retention indices taking into account the non-uniformity of the contributions of methyl and carbonyl substituents in thiophenes and furans was suggested. The indices of 12 unknown substances of these classes were calculated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 70–75, January, 1994.This work was carried out with financial support from the Russian fundamental Research Fund (project No. 93-03-4969).     

Chemical thermodynamics of polyaromatic compounds containing heteroatoms and five-membered rings

An analysis of chemical thermodynamic properties of gaseous polynuclear aromatic compounds containing N-, S-, and O-heteroatoms and five-membered rings is presented. Standard enthalpies of formation, entropies and heat capacities taken from the literature, or derived from appropriate data, serve as the data base for this analysis. Enthalpies of formation are used to compute empirical resonance energies for polynuclear heteroaromatic structures which, in turn, allow critical examination of this property. An additive method is described for estimating entropies and heat capacities. New or revised values for thermodynamic properties for a number of polyaromatic substances are presented and recommended values for some common polyaromatics are given.     

Electrophilic aromatic substitutions of silylated furans and thiophenes with retention of the organosilyl group

The influence of trialkylsilyl groups on the nucleophilic reactivities of furans and thiophenes is determined by kinetic experiments.     

Palladium-catalyzed one-pot synthesis of highly substituted furans by a three-component annulation reaction

A new three-component cyclization-coupling reaction catalyzed by palladium was developed, producing polysubstituted furans in good yields from readily available substrates. The reaction conditions and the scope of the process were examined, and a possible mechanism is proposed.     

Synthesis of enantiopure helical cyclophanes containing five-membered heterocyclic rings

The preparation of optically active (S)-(+)-4-(2-propenyl)[2.2]paracyclophane 1b is described. Cycloaddition reactions of this diene with N-phenylmaleimide 2 and maleic anhydride 5 were carried out under high pressure conditions. The cycloadducts were converted into optically active heterohelicenophanes. A systematic ¹H and ¹³C NMR spectroscopic analysis of the reaction products is also presented.