Universität Wien / University of Vienna (@univie.ac.at)

Controlling chemical reactions more efficiently and sustainably A team at the University of Vienna, led by chemist Nuno Maulide, has developed a groundbreaking method for controlling chemical reactions in a more targeted & efficient manner. 🧪 The study was published in @jacs.acspublications.org ⤵️

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Cation Sampling Enables Regiodivergent Distal Functionalization of Ketones Despite notable progress in catalytic olefin isomerization processes enabling distal Csp3–H functionalization, most methods depend on complex metal-based catalytic systems and face inherent challenges in achieving regiodivergent outcomes. Herein, we present a conceptually distinct approach in which we leverage cationic olefin isomerization for regiodivergent Csp3–H functionalization, wherein the selectivity results from a ketone-assisted process we term cation sampling. This method enables site-selective regiodivergent functionalization of sp3-hybridized carbons, allowing the formation of C–heteroatom bonds in challenging positions and unlocking access to products previously unattainable through metal-based methodologies. Detailed mechanistic studies support the proposed reaction pathway, which involves the engagement of two key oxocarbenium species that govern the regioselectivity of this process. https://pubs.acs.org/doi/10.1021/jacs.6c05299