The Hydrolysis of Ethyl 1-Methyl-2,4-cyclopentadiene-1-carboxylate by Nonenzymatic and Enzymatic Methods. Carbon-Carbon vs. Carbon-Oxygen Bond Cleavage

Article Article scientifique Article The Hydrolysis of Ethyl 1-Methyl-2,4-cyclopentadiene-1-carboxylate by Nonenzymatic and Enzymatic Methods. Carbon-Carbon vs. Carbon-Oxygen Bond Cleavage eng 1987-05-06 author Burger Ulrich 25497 author Erne-Zellweger Dominique author Mayerl-Affentranger Christa 30656 587-592 10.1002/hlca.19870700311 0018-019X https://onlinelibrary.wiley.com/doi/10.1002/hlca.19870700311 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. Dewey 540 36 Département de chimie organique 141 false Helvetica chimica acta 70 3 d8d97f72-c240-4df2-b6f7-a85deebbfd35 Article (Published version) Public Burger_HCA_198770587.pdf 453133 application/pdf openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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The Hydrolysis of Ethyl 1-Methyl-2,4-cyclopentadiene-1-carboxylate by Nonenzymatic and Enzymatic Methods. Carbon-Carbon vs. Carbon-Oxygen Bond Cleavage	Helvetica chimica acta			1987	172	249

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Mayerl-Affentranger, Christa