Site selective gold(i)-catalysed benzylic C-H amination via an intermolecular hydride transfer to triazolinediones

Kevin Bevernaege, Nikolaos V Tzouras, Albert Poater, Luigi Cavallo, Steven P. Nolan, Fady Nahra, Johan M. Winne

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Triazolinediones are known as highly reactive dienophiles that can also act as electrophilic amination reagents towards enolisable C-H bonds (ionic pathway) or weak C-H bonds (free radical pathway). Here, we report that this C-H amination reactivity can be significantly extended and enhanced via gold(i)-catalysis. Under mild conditions, several alkyl-substituted aryls successfully undergo benzylic C-H aminations at room temperature. The remarkable site selectivity that is observed points towards strong electronic activation and deactivation effects, that go beyond a simple weakening of the C-H bond. The observed catalytic C-H aminations do not follow the expected trends for a free radical-type C-H amination and show complementarity to existing methods. Density functional theory (DFT) calculations and distinct experimental trends provide a clear mechanistic rationale for observed selectivity patterns, postulating a novel pathway for triazolinedione-induced aminations via a carbon-to-nitrogen hydride transfer.
Original languageEnglish (US)
JournalChemical Science
DOIs
StatePublished - Aug 24 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-09-18
Acknowledgements: We are grateful to the The Research Foundation – Flanders (FWO) and the BOF (starting and senior grants to SPN) as well as the iBOF C3 project for financial support. The FWO is also acknowledged for Fundamental Research PhD fellowships to KB (11E1122N) and NVT (11I6921N). The FWO is also acknowledged by JMW for financial support (G005720N). A. P. thanks the Spanish Ministerio de Ciencia e Innovación for project PID2021-127423NB-I00. A. P. is a Serra Húnter Fellow and ICREA Academia Prize 2019.

ASJC Scopus subject areas

  • General Chemistry

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