Intermolecular vs. Intramolecular carbene reactions of a cage-functionalized cyclopentylcarbene

✍ Scribed by Alan P. Marchand; Kaipenchery A. Kumar; Kata Mlinarić-Majerski; Jelena Veljković

• Book ID: 104208938
• Publisher: Elsevier Science
• Year: 1998
• Tongue: French
• Weight: 506 KB
• Volume: 54
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(98)00909-0

✦ Synopsis

The results of carbene reactions of pentacyclo [5.4.0.02,6.03,10.oS,9]undecan-8ylidene (i.e., PCU-8-ylidene, 9), generated under different conditions by using different precursors [i. e., (i) sodium salt of PCU-8-one p-tosylhydrazone ( ), (ii) PCU-8-diazirine (11), and (iii) 8,8dibromo-PCU ( )], are reported. PCU-8-carbene (9), generated thermally from 8, afforded homopentaprismane (17, 9.6% yield) via intramolecular C-H insertion along with other reaction products. By way of contrast, photodecomposition of 11 afforded a mixture of isomeric azines, 21a-21d, as the major reaction product. No intramolecular carbene trapping products were obtained when 9 was generated via reaction of 12 with n-BuLl.