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Die Hydrolyse von 6 exo ‐substituierten 2 exo ‐ und 2 endo ‐Norbornylestern der p ‐Toluolsulfonsäure. Norbornanreihe. 3. Mitteilung
Author(s) -
Fischer Walter,
Grob Cyril A.,
Von Sprecher Georg,
Waldner Adrian
Publication year - 1980
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19800630422
Subject(s) - chemistry , 2 norbornyl cation , substituent , epimer , stereochemistry , nucleophile , hydrolysis , acetaldehyde , norbornane , medicinal chemistry , organic chemistry , ethanol , catalysis
The Hydrolysis of 6 exo ‐Substituted 2 exo ‐ and 2 endo ‐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.