Synthesis of a highly strained permethylenated cycloocta-1,5-diyne derivative by acid-catalysed thermal rearrangement

Preparation of a dimeric derivative of 1,1,2,2-tetraethynylethane (3,4-diethynylhexa-1,5-diyne) and its unexpected rearrangement to a permethylenated cycloocta-1,5-diyne, the structure of which was confirmed by X-ray crystallography, is reported.

[1]  F. Diederich,et al.  1,1,2,2‐Tetraethynylethanes: Synthons for Tetraethynylethenes and Modules for Acetylenic Molecular Scaffolding , 1996 .

[2]  F. Diederich,et al.  Macrocyclic Tetraethynylethene Molecular Scaffolding: Perethynylated aromatic dodecadehydro[18]annulenes, antiaromatic octadehydro[12]annulenes, and expanded radialenes , 1995 .

[3]  François Diederich,et al.  Carbon scaffolding: building acetylenic all-carbon and carbon-rich compounds , 1994, Nature.

[4]  F. Diederich,et al.  Stable [12]‐ and [18]Annulenes Derived from Tetraethynylethene , 1993 .

[5]  A. P. Marchand,et al.  Pinacol condensation of homocubanone. Synthesis and chemistry of homocubylidenehomocubane , 1991 .

[6]  R. Harvey,et al.  REDUCTIVE METHYLATION OF POLYCYCLIC AROMATIC QUINONES , 1980 .

[7]  T. Pilati,et al.  The structure and electron density of sym‐dibenzo‐1,5‐cyclooctadiene‐3,7‐diyne by X‐ray analysis at three different temperatures , 1977 .

[8]  R. Hoffmann,et al.  Carben‐Reaktionen, X. Ionische Zwischenstufen der Reaktion von Orthoameisensäure‐trimethylester mit Arylisocyanat , 1977 .

[9]  H. Roesky,et al.  5-Oxo-1,3λ4,2,4-dithiadiazole—A Five-Membered Heterocyclic Ketone† , 1975 .

[10]  J. Wirz,et al.  1,5-Cyclooctadiyne. Preparation and Reactivity , 1975 .

[11]  P. Garratt,et al.  Unsaturated eight-membered ring compounds. XI. Synthesis of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne and sym-dibenzo-1,3,5-cyclooctatrien-7-yne, presumably planar conjugated eight-membered ring compounds , 1974 .

[12]  Yoshinari Tanaka,et al.  Skipped diynes. V. Secondary diethynyl carbinols. Base-catalyzed ynol to enol rearrangements and ultraviolet spectra and conjugation , 1974 .

[13]  J. Wirz,et al.  1,5‐Cyclooctadiyne , 1973 .

[14]  K. Sisido,et al.  Syntheses of all of the racemic diastereoisomers of phytosphingosine , 1970 .

[15]  J. Josan,et al.  Derivatives of orthoacids. IV. Acid-catalysed thermal eliminations and baseinduced eliminations of some 2-Ethoxy-1,3-dioxolans , 1968 .

[16]  G. Crank,et al.  Derivatives of orthoacids. II. The preparation of olefins from 1,2-diols , 1964 .

[17]  A. S. Hay.  Oxidative Coupling of Acetylenes. II1 , 1962 .