2026-04-03T22:15:30Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/283402026-03-04T09:09:06Zcom_2072_452955com_2072_2054col_2072_453073

Desymmetrization of Malonic Monoesters and Malonic Acids via Enantioselective Catalytic C(sp3)─H Oxidation Siakavaras, Nikos Call Quintana, Arnau Bietti, Massimo Costas Salgueiro, Miquel European Commission Malonate derivatives are readily available starting materials widely employed in the synthesis of bioactive compounds. Herein, we report a novel catalytic protocol for the direct desymmetrization of malonic acids via enantioselective C(sp³)─H bond functionalization. Highly enantioselective (up to >99% ee) γ- and δ- C─H bond lactonization of readily available malonic acid monoesters and malonic acids is achieved, using manganese catalysts and hydrogen peroxide as the oxidant. Owing to the ease and versatility of malonic acid derivative synthesis, combined with the potential post-oxidation elaboration, this methodology overcomes the inherent lack of reactivity of the electron-poor C(sp³)─H bonds of this class of substrates against electrophilic oxidants to provide straightforward access to a broad range of quaternary stereocenters that can be orthogonally manipulated. Research funding: European Research Council. Grant Number: 883922, Spain Ministry of Science & Generalitat de Catalunya 2026-02-17 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion peer-reviewed http://hdl.handle.net/10256/28340 41703703 22209874 https://hdl.handle.net/10256/28340 eng info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.1030779 info:eu-repo/semantics/altIdentifier/issn/1433-7851 info:eu-repo/semantics/altIdentifier/eissn/1521-3773 info:eu-repo/grantAgreement/EC/H2020/883922/EU/Enantioselective C-H Oxidation Guided by Rational Catalyst Design/ECHO-GRACADE Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess application/pdf Wiley Angewandte Chemie International Edition, 2026, vol. undef, núm. undef, p. e1030779 Articles publicats (D-Q)