Struktur und Komplexbildung kleiner 1,3-dithiol-anellierter Thiakronenverbindungen

Gloe, Karsten; Krüger, Torsten; Stephan, Holger; Wagner, Michael R.; Drutkowski, U.; Olk, Ruth‐Maria; Leckelt, Ulrich; Richter, R.; Hoyer, Eberhard

doi:10.1002/(sici)1521-3749(199801)624:1<152::aid-zaac152>3.0.co;2-q

Cited by 8 publications

(2 citation statements)

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“…<1%) . Furthermore, while C s -symmetry TCC ( 10 ) is not a conformational possibility for simple cis- cyclononene (at least according to the MM3 and B3LYP vibrational frequency calculations), it too can be found in the CCDB, given the appropriate substituents and ring heteroatoms …”

Section: Resultsmentioning

confidence: 99%

cis-Cyclononene Conformational Families and a Crystallographic Example of a Skew-Chair−Boat Type-2 Conformation

et al. 2002

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Cyclononanes from the 7 low-energy conformational archetypal families (twist-boat[bond]chair, twist-chair[bond]boat, twist-chair[bond]chair, twist-chair[bond]twist-chair, skew-chair[bond]boat, skew-chair[bond]chair, and skew-boat[bond]boat) were transformed into 12 of 13 MM3 stochastically generated cis-cyclononenes. This was done by systematically converting single bond synclinal endocyclic torsion angles, one-at-a-time, into double-bond synperiplanar analogues, followed by geometry optimization [e.g. density functional theory B3LYP/6-31G(d)]. Torsion angles adjacent to the new double bond maintained their signs, while their magnitudes usually changed considerably to accommodate the new neighboring synperiplanar torsion angles. The six remaining torsion angles all maintained their signs and approximate magnitudes compared to corresponding values in the seven saturated parent structures. As a result, the same "twist"/"skew" conformational descriptors previously used for the saturated conformers can now also be applied to the corresponding unsaturated analogues. Three conformational families have multiple members (subtypes) in which the double bond is located at different positions on the same ring conformation. The solid-state structures of (+/-)-1-phenyl-1,3,4,5,6,7-hexahydro-2,6-benzoxazonine-6-carbonitrile (22) and (1RS,3SR)-1-phenyl-3-methyl-1,3,4,5,6,7-hexahydro-2,6-benzoxazonine-6-carbonitrile (23) were determined by single-crystal X-ray diffraction analysis. The asymmetric unit of the Ponemacr; unit cell for 22 contains two symmetry-unrelated molecules, both of which exhibit a skew-chair-boat (SCBtype-2) conformation identical to that found for crystalline 23. This subtype has yet to be found in the Cambridge Crystallographic DataBase. Crystal lattice packing considerations alone cannot explain the observation of the SCBtype-2 conformation since (1)H NMR spectroscopy shows the same conformational bias when the crystals are dissolved in CDCl(3).

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Section: Resultsmentioning

confidence: 99%

cis-Cyclononene Conformational Families and a Crystallographic Example of a Skew-Chair−Boat Type-2 Conformation

et al. 2002

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“…Als Modellbeispiele wurden dazu vier Derivate des Strukturtyps 2 ausgewählt, die ein 1,3-dithiol-anelliertes 9-Ringsystem mit wechselnder S,O-Donoratomkombination im Ring sowie an der Ligandperipherie enthalten. Die Kristallstrukturen von 2a [49], 2c [50] sowie zum Vergleich von 1 [37] [37] und der 1,3-dithiol -anellierten Thiakronenverbindungen 2a [49] und 2c [50] Abb. 6 Extraktion von Ag I mit 1,4,7-Trithiacyclononan 1 sowie den 1,3-dithiol-anellierten Thiakronenverbindungen 2a -d; …”

Section: 3-dithiol-anellierte Thiakronenverbindungenunclassified

Molecular Modeling-Studien schwefelhaltiger Wirt/Gast-Systeme

1999

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Thiacrown compounds: Synthesis and properties. (Review)

Литвинова¹,

Анисимов²

1999

Chem Heterocycl Compd

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Data of the last 15 vears on the synthesis and properties o/'vaiVous thiacrown compounds containing 2-8 sttlfttl" atoms in the ring are reviewed.The discovery of interesting and unique complexing charactcristics in crown ethers and their nitrogen and sulfur analogs is one of the most powcrful achievcments of modem organic chemistry. The selectivity of the macrocycle toward the ions of various mctals can be controllcd by the size of the ring, by the type, number, and position of the heteroatoms in the ring, and by the presence of functional groups in the ring and on its periphery. Of the many methods used in the synthcsis of crown ethers and their sulfur analogs (thiacrowns) the most successful is the reaction of dihalogcno dcrivatives with glycols and dithiols, by means of which it is possible to influence positively the main factors determining the selectivity of the macrocycle. Methods have been developed on the basis of this reaction for the synthesis of numerous sulfur-containing heterocyclic compounds.The various types of macrohcterocycles are of great interest as reagents that make it possible to extract metals with the object of separating thcir mixtures and subsequently determining the individual elements. Sulfurcontaining macroheterocycles and their open-chain analogs, called podands, occupy an important position in supramolocular chemistry, having the ability to connect selectively the ions of transition and heavy metals, such as Cu(II). The use of these compounds makes it possible to model the biological systems and processes in which organosulfur compounds participate. The use of macrocycles as the active components in the membranes of ionselective electrodes and molecular receptors has proved very promising.In the present review an attempt is made to summarize comprehensively the achievements of the last 10-15 years in the chemistry of thiacrown compounds containing only sulfur atoms as heteroatoms. The review is not concerned with the extensive material on the synthesis and properties of macroheterocycles containing nitrogen, oxygen, and other heteroatoms.

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Struktur und Komplexbildung kleiner 1,3-dithiol-anellierter Thiakronenverbindungen

Cited by 8 publications

References 3 publications

cis-Cyclononene Conformational Families and a Crystallographic Example of a Skew-Chair−Boat Type-2 Conformation

cis-Cyclononene Conformational Families and a Crystallographic Example of a Skew-Chair−Boat Type-2 Conformation

Molecular Modeling-Studien schwefelhaltiger Wirt/Gast-Systeme

Thiacrown compounds: Synthesis and properties. (Review)

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