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Lossen Rearrangement vs C–N Reductive Elimination Enabled by Rh(III)-Catalyzed C–H Activation/Selective Lactone Ring-Opening: Chemodivergent Synthesis of Quinolinones and Dihydroisoquinolinones

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journal contribution
posted on 04.12.2020, 12:35 by Mengyao Bian, Hamdulla Mawjuda, Hui Gao, Huiying Xu, Zhi Zhou, Wei Yi
An unprecedented Rh­(III)-catalyzed cascade C–H activation/Lossen rearrangement of aromatic amides with methyleneoxetanones has been realized along with a tunable C–N bond reductive elimination/trans esterification, giving divergent access to quinolinones and dihydroisoquinolinones via selective ring-opening of the four-membered lactone unit. Combined computational and experimental mechanistic studies defined the solvent-involved distinguished reaction paths, the origin of the observed chemodivergence, as well as the role of the substituent attached at the oxidizing directing group in tuning the reaction outcomes.