Preparation and Structures of Cyclic Tetrathiadienes and Tetrathiaenynes

Staeb, Tobias H.; Gleiter, Rolf; Röminger, Frank

doi:10.1002/1099-0690(200208)2002:16<2815::aid-ejoc2815>3.0.co;2-9

Cited by 20 publications

(18 citation statements)

References 14 publications

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“…After transformation of the hydroxyl group into tosylate, the reaction of 2 with cis-ethenedithiolate in dimethylformamide (DMF) solution afforded desired partially unsaturated 28-membered thiacrown ether 4, together with a small amount of 14membered thiacrown ether 3. Compound 3 was previously synthesized by the reduction of the corresponding cyclodiyne by Gleiter and co-workers [11]. In acetonitrile solution, however, the reaction did not proceed.…”

Section: Synthesis Of Partially Unsaturated Thiacrown Ethersmentioning

confidence: 99%

“…Thiacrown ethers that possess both saturated and unsaturated bonds in their ring systems are also interesting compounds on comparison of their conformation, electrochemical properties, and complexation behaviors with those of the corresponding saturated or unsaturated compounds. Among the thiacrown ethers that possess both saturated and unsaturated bonds, some 14membered cyclic compounds that possess alternating Z-carbon-carbon double bonds and propylene chains are known [9][10][11][12][13][14][15]. However, larger cyclic compounds featuring this system have not been synthesized so far.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, structure, and complexation behavior of 14‐ and 28‐membered partially unsaturated thiacrown ethers

Shimizu

Komatsuzaki

Hirabayashi

2011

Heteroatom Chemistry

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Section: Synthesis Of Partially Unsaturated Thiacrown Ethersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, structure, and complexation behavior of 14‐ and 28‐membered partially unsaturated thiacrown ethers

Shimizu

Komatsuzaki

Hirabayashi

2011

Heteroatom Chemistry

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“…According to [8], the heteroring conformation should be represented as [2525] with equatorial orientation of the methyl groups. Comparison of the molecular structures of compound II and isomeric tetrathiadiene with sulfur atoms at the double bonds [9] shows their essential similarity. An exception is the transannular distance between the sp 2 -carbon atoms, which is longer by 0.48 Å in molecule II.…”

mentioning

confidence: 99%

“…However, weaker interactions (as in its isomer [9]) give rise to cylindrical structures oriented along the b crystallographic axis (Fig. 2).…”

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confidence: 99%

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Two isomeric fourteen-membered bis-dithioacetals derived from (Z)- and (E)-but-2-ene-1,4-dithiols

et al. 2009

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Z)-But-2-ene-1,4-dithiol was found to undergo isomerization into the E isomer. Condensation of (Z)-and (E)-but-2-ene-1,4-dithiols with acetaldehyde gave isomeric fourteen-membered bis-dithioacetals whose structure was determined by X-ray analysis.The formation of monomeric and dimeric cyclic dithio acetals, as well as of polymeric products, is determined by the nature of initial α,ω-dithiol and carbonyl compound [1], and macrocyclic compounds with short hydrocarbon bridges between sulfur atoms are difficultly accessible [2]. While studying seven-membered unsaturated dithioacetals [3], we found that the condensation of but-2-ene-1,4-dithiol with acetaldehyde, apart from previously reported 2-methyl-1,3-dithiacyclohept-5-ene (I) [4], gives two minor products II and III which were isolated in low yields (2 and 3%, respectively; Scheme 1). The 1 H and 13 C NMR spectra of compounds I-III, recorded at low temperature, are fairly similar; the spectra indicated the presence of CH 2 CH=CHCH 2 and CH 3 CH fragments in their molecules. According to the X-ray diffraction data, compounds II and III are fourteen-membered bis-dithioacetals [5]. The formation of macrocyclic compound II might be expected [1], while the presence in the reaction mixture of its isomer III with E configuration at the double bond is difficult to predict and therefore special comment is necessary.Obviously, bis-dithioacetal III could be formed only as a result of condensation of (E)-but-2-ene-1,4-dithiol with acetaldehyde. Stereochemical 1 H NMR analysis [6] showed that the source of (E)-but-2-ene-1,4-dithiol is the corresponding Z isomer (which undergoes isomerization on storage as neat liquid) rather than (Z)-but-2-ene-1,4-diol, (Z)-1,4-dichlorobut-2-ene, and the corresponding dithioacetate [7].Molecule II is oriented along the 2 1 axis, so that only a half of the molecule is independent (Fig. 1). The bond lengths and bond angles therein are within the corresponding standard values. According to [8], the heteroring conformation should be represented as [2525] with equatorial orientation of the methyl groups. Comparison of the molecular structures of compound II and isomeric tetrathiadiene with sulfur atoms at the double bonds [9] shows their essential similarity. An exception is the transannular distance between the sp 2 -carbon atoms, which is longer by 0.48 Å in molecule II.Analysis of intermolecular interactions revealed neither shortened contacts nor hydrogen bonds in the crystalline structure of cis-tetrathiadiene II. However,

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Die Carbonyl⋅⋅⋅Tellurazol‐Chalkogenbindung als molekulare Erkennungseinheit: Von Modellstudien zu supramolekularen organischen Gerüstverbindungen

et al. 2020

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In den letzten Jahren entwickelten sich die Chalkogenbindungen, bei denen die Bindung über nicht‐kovalente Wechselwirkungen unter Beteiligung von Chalkogenzentren erfolgt, in zahlreichen Forschungsfeldern zu einer interessanten Alternative zu den weitverbreiteten Wasserstoffbrückenbindungen. Mittels quantenchemischer Berechnungen auf hohem Niveau konnte gezeigt werden, dass die Carbonyl⋅⋅⋅Tellurazol‐Chalkogenbindung mindestens so stark wie eine konventionelle Wasserstoffbrückenbindung ist. Durch die Verwendung des Carbonyl⋅⋅⋅Tellurazol‐Bindungsmotivs, das in Form von cyclischen Tellurazolpeptiden zum Einsatz kam, gelang uns das Design komplexer supramolekularer Netzwerke in der festen Phase. Röntgenstrukturanalysen belegen, dass die starre Struktur des Cyclopeptids auf Wasserstoffbrückenbindungen zurückzuführen ist, während das supramolekulare Netzwerk durch Chalkogenbindungen zusammengehalten wird. Die Erscheinungsform des supramolekularen Netzwerks hängt vom verwendeten Peptid ab; sowohl lineare Stränge als auch bienenwabenartige supramolekulare organische Gerüstverbindungen (SOF) konnten beobachtet werden. Die einzigartige SOF‐Struktur verfügt über zwei Kanäle, die mit verschiedenen Lösungsmittelgemischen gefüllt sind, die entweder eingeschlossen oder frei beweglich sind.

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Preparation and Structures of Cyclic Tetrathiadienes and Tetrathiaenynes

Cited by 20 publications

References 14 publications

Synthesis, structure, and complexation behavior of 14‐ and 28‐membered partially unsaturated thiacrown ethers

Synthesis, structure, and complexation behavior of 14‐ and 28‐membered partially unsaturated thiacrown ethers

Two isomeric fourteen-membered bis-dithioacetals derived from (Z)- and (E)-but-2-ene-1,4-dithiols

Die Carbonyl⋅⋅⋅Tellurazol‐Chalkogenbindung als molekulare Erkennungseinheit: Von Modellstudien zu supramolekularen organischen Gerüstverbindungen

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