2,7,9-trimethylenetricyclo[4.3.0.03,8]nonane and 2,9-dimethylenetricyclo[4.3.0.03,8]non-4-ene. Synthesis and properties

✍ Scribed by Gleiter, Rolf ;Herb, Thilo ;Borzyk, Oliver ;Hyla-Kryspin, Isabella

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 776 KB
• Volume: 1995
• Category: Article
• ISSN: 0947-3440
• DOI: 10.1002/jlac.199519950245

✦ Synopsis

Abstract

The synthesis of 2,7,9‐trimethylenetricyclo[4.3.0.0^3,8^]nonane (8), 7,9‐dimethylenetricyclo[4.3.0.0^3,8^]nonan‐2‐one (15), and 2,9‐dimethylenetricyclo[4.3.0.0^3,8^]non‐4‐ene (9) has been achieved. The first key step of the synthesis is a Diels‐Alder reaction. In the reaction sequence affording 8 and 15 the starting materials are 1,3‐cyclohexadiene (10) and acetylallene (11) and in the synthesis of 9 the diene 16 and methyl vinylketone (17). Further key steps are an intramolecular Paterno‐Büchi and an oxetane ring‐opening reaction. Compound 8 as well as 15 rearrange to the corresponding triquinane derivatives according to a Cope rearrangement. The PE spectra of 8, 9, and 15 reveal a considerable through‐space and through‐bond interaction of the double bonds.