A novel bicyclic ketal fragmentation reaction

✍ Scribed by Michael Bjorklund; Jong Gab Jun; Bradford P. Mundy

• Book ID: 104228833
• Publisher: Elsevier Science
• Year: 1985
• Tongue: French
• Weight: 240 KB
• Volume: 26
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)98681-7

✦ Synopsis

Bicyclic ketals of the 6,8-dioxabic clo[3.2.11octane series are specifically cleaved to give 6,E-unsaturated ketones by treatment o Y the ketal with acetyl iodide.

Bicyclic ketals of the 6,8-dioxabicyclo[3.2.1]octane series, (l), well-represented by the insect pheromones frontalin,(2), brevicomin, (3), and multistriatin, (4), have been found to be generally resistant to hydrolysis. Because methodologies are available to gain access to a host of substitution patterns having specific stereochemistries, it seemed that a useful endeavor should be directed towards the chemical modification of these readily-available, robust ketals.

We have already demonstrated a specific utility in the stereospecific conversion of 5 to 6, a component of the glandular secretion of the civet catl. We now show a potentially useful entry into 6,~ -unsaturated ketones. 6

1. All R-groups are H, unless indicated.