Spiropentadiene Explained

Spiropentadiene, or bowtiediene, is a hydrocarbon with formula . The simplest spiro-connected diene, it is very unstable - decomposing even below -100 °C - due to its high bond strain and does not occur in nature. Its synthesis was reported in 1991.[1] [2]

Synthesis

Spiropentadiene was synthesised from bistrimethylsilylpropynone 1 by reaction with p-toluenesulfonylhydrazide to tosylhydrazone 2 followed by treatment with sodium cyanoborohydride to allene 3 and followed by two successive reactions with chlorocarbene generated from methyllithium and dichloromethane to spiro compound 5. Spiropentadiene was trapped in a liquid nitrogen trap after reaction with TBAF in a double elimination reaction.

Derivatives

The derivative dichlorospiropentadiene has been reported.[3] An all-silicon derivative (Si5 frame, (tBuMe2Si)3Si side groups) is also known.[4] In contrast to the carbon parent this compound is stable with a melting point of 216 to 218 °C. The angle between the two rings as measured by X-ray single-crystal analysis is 78°.

Notes and References

  1. 10.1021/ja00013a067. Spiropentadiene. 1991. Billups . W. E.. Haley . M. M.. Journal of the American Chemical Society. 113. 13. 5084 .
  2. News: July 13, 1991 . Elusive bowtie pinned down - synthesis of spiropentadiene, a carbonaceous compound nicknamed bowtiediene because it is shaped like a bowtie . Science News . https://web.archive.org/web/20220216121520/https://www.thefreelibrary.com/Elusive+bowtie+pinned+down.-a011134368 . 2022-02-16.
  3. 10.1016/S0040-4039(99)01293-9. Synthesis and characterization of 1,4-dichlorospiropentadiene. 1999. Saini . R.. Litosh . V.. Daniels . A.. Billups . W.. Tetrahedron Letters. 40. 34. 6157 .
  4. 10.1126/science.290.5491.504. A Stable Bicyclic Compound with Two Si=Si Double Bonds. 2000. Iwamoto . T.. Science. 290. 504–506. Tamura . M.. Kabuto . C.. Kira . M.. 11039928. 5491 . 2000Sci...290..504I .