Die Hydrolyse von 6exo-substituierten 2exo- und 2endo-Norbornylestern der p-Toluolsulfonsäure. Norbornanreihe. 3. Mitteilung

✍ Scribed by Walter Fischer; Cyril A. Grob; Georg Von Sprecher; Adrian Waldner

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: German
• Weight: 604 KB
• Volume: 63
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19800630422

✦ Synopsis

The Hydrolysis of 6**exo‐Substituted 2exo‐ and 2endo‐Norbornyl** **p‐Toluenesulfonates. Norbornane Series. Part 3**

Hydrolysis of the 6__exo__‐substituted 2__exo__‐ and 2__endo__‐norbornyl p‐toluenesulfonates 1b‐1 and 2b‐1, respectively, in 70% dioxane led to different amounts of the following products: Unrearranged 2__exo__‐norbornanols 3 and norbornenes 5, accompanied in somes cases by small amounts of the rearranged R__endo__‐epimers 4 and 6 and by norticyclenes 7. When the 6__exo__‐substituent was a nucleophilic group as in 1e‐1 and 2e‐1, various amounts of tricyclic products were also formed by endo‐cyclization. These results show that the 2__exo__‐ and 2__endo__‐esters 1 and 2, respectively, react by way of different intermediates. In cases where the 6__exo__‐substituent was an n‐electron donor, as in 1m‐r and 2m‐r, quantitative fragmentation to (3‐cyclopentenyl)acetaldehyde (13) occurred.