1,5‐Cyclooctadiyne. Preparation and Reactivity

Kloster‐Jensen, Else; Wirz, Jakob

doi:10.1002/hlca.19750580121

Cited by 80 publications

(34 citation statements)

References 51 publications

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“…This analysis was confirmed by 1 H NMR spectroscopic investigations on the diatropicity and paratropicity of related macrocycles. Electrochemical studies were also in agreement with these findings [15]: octadehydro [12]annulene 5b undergoes two stepwise one-electron reductions (EЊ ¼ -0.99 and -1.46 V vs. Fc/Fc þ (ferrocene/ferricinium couple) in THF) more readily than the dodecadehydro [18]annulene 6a (EЊ ¼ -1.12 and -1.52 V). This redox behavior is best explained with the formation of an aromatic (4n þ 2) -electron dianion from antiaromatic 5b, whereas 6a loses its aromaticity upon reduction (Scheme 2).…”

supporting

confidence: 80%

“…Oxidative Glaser-Hay macrocyclization of cis-bis(trialkylsilyl)-protected TEEs yielded the per(silylethynyl)ated octadehydro [12]annulenes 5a/b and dodecadehydro [18]annulenes 6a/b [13]. Both annulene perimeters are perfectly planar according to X-ray crystal structure analysis [14].…”

Section: Macrocyclic Acetylenic Scaffoldingmentioning

confidence: 96%

“…Macrocyclic acetylenic scaffolding yielded perethynylated antiaromatic octadehydro [12]annulenes and aromatic dodecadehydro [18]annulenes as well as highly stable expanded radialenes with extended all-carbon cores. An attempted new synthesis of perethynylated octadehydro [12]annulenes was unsuccessful and led to the isolation of a highly strained permethylenated cycloocta-1,5-diyne instead.…”

mentioning

confidence: 99%

“…A detailed analysis of the UV/Vis spectra revealed that the yellow-colored [18]annulenes 6a/b, with a large HOMO-LUMO gap (2.57 eV in pentane), are aromatic, whereas the purple-colored [12]annulenes 5a/b, with a smaller HOMO-LUMO gap (1.87 eV), are antiaromatic. This analysis was confirmed by 1 H NMR spectroscopic investigations on the diatropicity and paratropicity of related macrocycles.…”

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confidence: 99%

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Functional acetylenic molecular architecture

Diederich¹

1999

Pure and Applied Chemistry

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A diversity of perethynylated building blocks, in particular derivatives of tetraethynylethene (TEE, 3,4-diethynylhex-3-ene-1,5-diyne), were prepared for the construction of multinanometer-sized functional molecular objects. Macrocyclic acetylenic scaffolding yielded perethynylated antiaromatic octadehydro [12]annulenes and aromatic dodecadehydro [18]annulenes as well as highly stable expanded radialenes with extended all-carbon cores. An attempted new synthesis of perethynylated octadehydro [12]annulenes was unsuccessful and led to the isolation of a highly strained permethylenated cycloocta-1,5-diyne instead. Acyclic acetylenic scaffolding using both TEEs and 1,2-diethynylethenes (DEEs (E)-hex-3-ene-1,5-diynes) afforded the first oligomers and polymers with the poly(triacetylene) backbone [PTA, -(CϵC-CR¼CR-CϵC) n -]. The effective conjugation length for this third class of linearly conjugated polymers with a nonaromatic all-carbon backbone, besides polyacetylene and poly(diacetylene), was determined to be in the range of 7-10 monomeric units. By lateral attachment of dendrons along the conjugated backbone of PTA oligomers, cylindrically shaped dendrimers were obtained which can be viewed as insulated molecular wires. Donoracceptor substituted arylated TEEs and DEEs were prepared, and their unusual electrochemical properties and tendency to undergo photochemical trans → cis isomerization were investigated. Measurements of third-order nonlinear optical effects by third harmonic generation revealed useful structure-function relationships. The highest second hyperpolarizabilities ␥ were obtained for two-dimensionally fully conjugated systems with reduced molecular symmetry. PERETHYNYLATED BUILDING BLOCKS FOR MODULAR CHEMISTRYAcetylenic molecular scaffolding in one, two, and three dimensions aims at producing new nanoscale molecular and polymeric materials that exhibit unusual electronic and optical function and properties. These efforts have greatly benefited from the recent renaissance in preparative acetylene chemistry [1] and, in particular, from the discovery of novel metal-catalyzed cross-coupling reactions for C-C bond formation [2]. A rich variety of peralkynylated building blocks have been prepared as starting materials in this modular synthetic approach to new advanced materials [3][4][5][6] and, among these, derivatives of tetraethynylethene (1, TEE, 3,4-diethynylhex-3-ene-1,5-diyne) [7][8][9] are particularly useful. Today, TEEs of nearly any desired functionalization and silyl-protection are available. Additional perethynylated chromophores such as the [3]radialene 2 [10] and [3]cumulene 3 [11] have been prepared in our laboratory. On the other hand, all efforts to synthesize the perethynylated allene 4, a precursor to threedimensional networks and for formation of helical polymers, have failed in the past [12] (Scheme 1). MACROCYCLIC ACETYLENIC SCAFFOLDINGOxidative Glaser-Hay macrocyclization of cis-bis(trialkylsilyl)-protected TEEs yielded the per(silylethynyl)ated octadehydro [12]annulenes...

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supporting

confidence: 80%

Section: Macrocyclic Acetylenic Scaffoldingmentioning

confidence: 96%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Functional acetylenic molecular architecture

Diederich¹

1999

Pure and Applied Chemistry

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“…103 This finding is probably a result of the perfect suitability of the radialene 27 for subsequent Diels-Alder 85,86,87 reactions since all exocyclic double …”

Section: Tetrafluorobutatriene -Dimersmentioning

confidence: 99%