Syntheses and properties of the [2n]Cyclophanes

Boekelheide, V.

doi:10.1007/3-540-12397-0_2

Cited by 90 publications

(55 citation statements)

References 192 publications

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“…[4][5][6] As far as the chemical behavior is concerned the vast majority of the reported reactions has been carried out at the benzene rings. The chemistry of the molecular bridges of these molecules should also be interesting, especially when the bridges carry important functional groups.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3] Since then, most studies have been devoted to elucidation of the structural characteristics of [2.2]paracyclophanes, particularly their geometry and steric properties, transanular interactions, and ring strain. [4][5][6] As far as the chemical behavior is concerned the vast majority of the reported reactions has been carried out at the benzene rings. The chemistry of the molecular bridges of these molecules should also be interesting, especially when the bridges carry important functional groups.…”

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confidence: 99%

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Reduction of Pseudo-geminal Bis(ethynyl)-Substituted [2.2]Paracyclophanes

Sarbu¹,

Hopf²,

Grunenberg³

et al. 2014

Synlett

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The reduction of pseudo-geminal bis(ethynyl)-substituted [2.2]paracyclophanes provides compounds with new bridges. The type of bridging is substituent dependent. The (trimethylsilyl)ethynyl moiety induces the formation of a bridge with two semicyclic double bonds; less bulky substituents, like propynyl and phenylethynyl, lead to bridges with endo double bonds.Key words acetylenes, reduction, dienes, lithium, paracyclophanes [2.2]Paracyclophane derivatives have been the subject of particular interest since their first appearance in the literature more than six decades ago.1-3 Since then, most studies have been devoted to elucidation of the structural characteristics of [2.2]paracyclophanes, particularly their geometry and steric properties, transanular interactions, and ring strain. [4][5][6] As far as the chemical behavior is concerned the vast majority of the reported reactions has been carried out at the benzene rings. The chemistry of the molecular bridges of these molecules should also be interesting, especially when the bridges carry important functional groups. In the last several years we have developed several methods for the introduction of new bridges into [2.2]paracyclophanes. 7 Although we reported the incorporation of various functional groups into the ethano bridges of [2.2]paracyclophanes, 8 the chemistry of this type of bridge has received little attention so far.Functional groups in pseudo-geminally substituted [2.2]paracyclophanes often undergo highly specific reactions. This is due to the rigid framework and the short distance within the aromatic units. In one such application, unsaturated cyclophane bis(esters) provided the corresponding ladderanes by intramolecular photocyclization. 9-11The 4,13-bis(ethynyl)[2.2]paracyclophane and its derivatives are interesting building blocks for molecular scaffolding, 12 since the ethynyl functions can easily be connected by various coupling reactions.Pentalenes represent another class of hydrocarbons with an impressive chemical history. 13 The development of the chemistry of these antiaromatic 4n hydrocarbons was strongly correlated with the number of efficient synthetic methods for the preparation of these compounds. A general route to dibenzopentalenes is represented by the metal-induced dimerization of different types of ethynyl aromatics. 14 For example, the reduction of tris(isopropyl)silylethynylbenzene (1) with excess lithium, followed by oxidation with iodine provided the dibenzo[a,e]pentalene derivative 2 in 7% yield (Scheme 1). 15 Scheme 1Prompted by these recent developments on the chemistry of pentalenes, we decided to investigate the reactions of a series of pseudo-geminally substituted bis(ethynyl) derivatives with lithium. Thus, we are presenting here a preliminary report on the interaction of lithium with 4,13-bis(trimethylsilyl)-, 4,13-bis(propyn-1-yl)-, and 4,13-bis(phenylethynyl)[2.2]paracyclophanes.In a first experiment we have used as substrate an ethynyl aromatic compound related to 1, 4,13-bis(trimethylsilyl)[2.2]paracyclo...

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Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

Reduction of Pseudo-geminal Bis(ethynyl)-Substituted [2.2]Paracyclophanes

Sarbu¹,

Hopf²,

Grunenberg³

et al. 2014

Synlett

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“…Arenophanes, especially cyclophane ( [2,2]paracyclophane), are interesting compounds not only because of mere synthetic interest and their usage in some fields but also due to their striking properties, such as the possibility of interaction of the π-electron system of two or more arene decks, to generate a new overall π-electron system so that some properties exhibited by them are totally π-electron system different from the corresponding individual arene decks (21)(22)(23)(24).…”

Section: Introductionmentioning

confidence: 99%

Isomeric Structures of Furoxan-Fused [2,2]paracyclophane—A DFT Study

Türker

Gümüş

2012

Polycyclic Aromatic Compounds

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The present study theoretically deals with furoxan-fused [2,2]paracyclophane systems and some structures possibly involved in their isomerization processes. These intermediate structures are certain di-and tetra-nitroso derivatives and systems having dioxadiazatidine ring(s). Computationally, B3LYP/6-31G(d,p) level of density functional theory has been employed. Certain properties of the systems, such as geometries, energies, and aromaticity of the benzenoid rings, are harvested and discussed.

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“…Varieties of [3.3]metacyclophanes containing oxygen [4] and nitrogen [5] as a hetero atom have also been reported. In general, cyclic compounds such as small sized metacyclophanes have various conformations derived from their orientations of the aromatic parts [6]. As part of our ongoing research towards the synthesis and conformational analysis of various substituted [3.3]metacyclophanes [7] [8], in this study, we report the synthesis and absolute structure determination of two novel small-sized metacyclophanes having thiaether bridges and ethynyl substituents.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Molecular Structures of Two Novel π-Conjugation Extended Dithia[3.3]metacyclophanes

Moriguchi¹,

Yakeya²,

Jalli³

et al. 2017

CSTA

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Two novel dithia [3.3]metacyclophanes substituted with ethynyl groups were synthesized as small-sized metacyclophanes from the corresponding brominated dithia-metacyclophanes via C-C bond formation reaction. These compounds were characterized by using 1 H NMR, mass spectrometry and elemental analyses. The exact structures were determined by using X-ray diffraction analyses. X-ray diffraction analysis results revealed that these compounds have anti conformations because of existence of intermolecular π-π interaction and some short contacts in the crystal. The long wavelength fluorescence was observed for one of the compound having a pyrene moiety in solid state because of the existence of the intermolecular π-π interaction between two pyrene units.

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Syntheses and properties of the [2n]Cyclophanes

Cited by 90 publications

References 192 publications

Reduction of Pseudo-geminal Bis(ethynyl)-Substituted [2.2]Paracyclophanes

Reduction of Pseudo-geminal Bis(ethynyl)-Substituted [2.2]Paracyclophanes

Isomeric Structures of Furoxan-Fused [2,2]paracyclophane—A DFT Study

Synthesis and Molecular Structures of Two Novel π-Conjugation Extended Dithia[3.3]metacyclophanes

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