ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The title ester 5 is shown to undergo C-C bond cleavage under the conditions of basic ester hydrolysis (KOH/EtOH) with formation of potassium ethyl carbonate (6) and the tautomeric methylcyclopentadienes 7 and 8. In contrast, porcine liver esterase (PLE, EC 3.1.1.1) cleanly hydrolyses 5 to give the isolable 1-methyl-2,4-cyclopentadiene-1-carboxylic acid (13). The latter undergoes thermal dimerization with conservation of the geminal-substitution pattern. The configuration of the Diels-Alder adduct 17 is ascertained by it photochemical transformation into bishomocubane dicarboxylic acid 12, easily distinguished by its C2 symmetry. Under the conditions of acid-catalyzed hydrolysis, dimerization of ester 5 and polymerization prevail, unless low acid concentration is used. The dimer 9 of 5 has one ester function that is reluctant to undergo basic hydrolysis.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19870700311
Permalink
