(Z)‐3,7‐Bis(phenylsulfonyl)pentacyclo‐[5.1.0.0^2,4.0^3,5.0^6,8]octan, ein Octabisvalen‐Derivat

Abstract

Octabisvalen, (CH)8, ist das noch unbekannte dritte gesättigte und hochgespannte Valenzisomer von Cyclooctatetraen. Als erstes kristallines Derivat konnte 1, XSO2C6H5, aus cis‐Benzoltrioxid synthetisiert werden. 1 ist bis ca. 200°C beständig.

Synthesis and Applications of Bicyclo[1.1.0]butyl and Azabicyclo[1.1.0]butyl Organometallics

“…The most common heteroatom‐based electrophiles that have been used as reaction partners with metalated bicyclo[1.1.0]butanes are silyl chlorides, exemplified by the work of Ando [81–82] and Rücker [83–84] . Although this type of reactivity has been demonstrated on numerous systems, the relative inertness of the resulting C−Si bond has limited the synthetic potential of such species.…”

“…[74] The most common heteroatom-based electrophiles that have been used as reaction partners with metalated bicyclo[1.1.0]butanes are silyl chlorides, exemplified by the work of Ando [81][82] and Rücker. [83][84] Although this type of reactivity has been demonstrated on numerous systems, the relative inertness of the resulting CÀ Si bond has limited the synthetic potential of such species. However, this reactivity was uniquely harnessed by Szeimies and coworkers in 1986 in an attempt to explore the scope of heteroatom-based electrophiles that can react with metalated bicyclo[1.1.0]butanes (Scheme 7a).…”

125 Jahre Chemie im Spiegel der “Angewandten”

“…Beispiele theoretisch interessanter Moleküle in der Angewandten Chemie aus den 1960er bis 1980er Jahren. a) Bullvalen, [198] b) 1,6-Methano [10]annulen, [196] c) das intermediär nachgewiesene kleinste Dehydroannulen, [199] d) ein stabiles niedrig substituiertes Pentalen, [200] e) ein stabiles Tetrahedran, das über Rçntgenstrukturanalyse charakterisiert wurde, [201] f) Hexaethinylbenzol, [202] g) ein Octabisvalen, [203] h) Stellatrien, [204] i) ein Tetraphosphacuban. [205] 125 Jahre Angewandte Chemie (Tabelle 8), in den anschließenden Jahren dieses neue Gebiet der Annulenchemie in eindrücklicher Weise.…”

125 Years of Chemistry in the Mirror of “Angewandte”

“…[216] Toward the end of this period, a review by Jerome H. Perlstein on "Organic Metals-The Intermolecular Migration of Aromaticity" indi- Figure 10. Examples of theoretically interesting molecules in Angewandte Chemie from the 1960s to the 1980s: a) bullvalene, [198] b) 1,6methano [10]annulene, [196] c) the smallest dehydroannulene detected as an intermediate, [199] d) a stable low-substituted pentalene, [200] e) a stable tetrahedrane, which was characterized by X-ray crystal-structure analysis, [201] f) hexaethynylbenzene, [202] g) an octabisvalene, [203] h) stellatriene, [204] i) a tetraphosphacubane. [205] cated the way forward towards advanced organic materials.…”