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Precise Control of the Site-Selectivity in Ruthenium-Catalyzed C-H Bond Amidations by Cyclic Amides as Powerful Directing Groups

Abstract : Selective C-H functionalizations aiming at the formation of new C-N bonds is of paramount importance in the context of step-and atom-economy methodologies in organic synthesis. Although the implementation of noble metal catalysts is prevalent, more benign cobalt pre-catalysts have recently appeared promising. However, they sometimes feature selectivity issues that limits its applicability in late-stage functionalization. Herein, we report on a highly reactive ruthenium-based catalytic system displaying excellent levels of mono-, regio-and site-selectivity exploiting a series of biologically-relevant cyclic amides as weak directing groups. The use of dioxazolone derivatives as the amidating reagent overcomes the issues encountered in the use of unstable azide derivatives for such transformations and it enables to perform these reactions under very mild reaction conditions (air, 40 o C). Moreover, a combination of deuteration experiments and a comparative study with different types of directing groups highlight the relevance of weak amide directing groups for enabling formation of six-membered cycloruthenate intermediates in key elementary steps of the catalytic cycle. In addition, DFT computational calculations were carried out for the first time for studying ruthenium-catalyzed C-N bond-forming processes via C-H activation assisted by weak directing groups, thereby elucidating the origin of the regio-and site-selectivity.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-03841084
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Submitted on : Sunday, November 6, 2022 - 6:00:05 PM
Last modification on : Tuesday, November 8, 2022 - 4:07:48 AM

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Yu-Chao Yuan, Qiu-Li Lu, Xiao-Tong Zhu, Sergio Posada-Pérez, Miquel Solà, et al.. Precise Control of the Site-Selectivity in Ruthenium-Catalyzed C-H Bond Amidations by Cyclic Amides as Powerful Directing Groups. Organic Chemistry Frontiers, In press, ⟨10.1039/D2QO01434C⟩. ⟨hal-03841084⟩

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