Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

"This is the peer reviewed version of the following article: Oliver-Tomas, Borja, Michael Renz, and Avelino Corma. 2017. Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids. Chemistry - A European Journal 23 (52). Wiley: 12900 908. doi:10.1002/chem.201702680, which has been published in final form at https://doi.org/10.1002/chem.201702680. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a -keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the -position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing -proton atoms. Hence, the latter are suitable to react through the -keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2% yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the -keto acid intermediate.The authors thank MINECO (CTQ2015-67591-P and Severo Ochoa program, SEV-2016-0683) and Generalitat Valenciana (PROMETEO II/2013/011 Project) for funding this work. B.O.-T. is grateful to the CSIC (JAE program) for his PhD fellowship.Oliver-Tomás, B.; Renz, M.; Corma Canós, A. (2017). Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids. Chemistry - A European Journal. 23(52):12900-12908. https://doi.org/10.1002/chem.201702680S12900129082352Renz, M. (2005). Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope. European Journal of Organic Chemistry, 2005(6), 979-988. doi:10.1002/ejoc.200400546Pham, T. N., Sooknoi, T., Crossley, S. P., & Resasco, D. E. (2013). 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