Electrophilic Iron Catalyst Paired with a Lithium Cation Enables Selective Functionalization of Non‐Activated Aliphatic C−H Bonds via Metallocarbene Intermediates

Abstract

Combining an electrophilic iron complex [Fe( F pda)-(THF)] 2 (3)[ F pda = N,N'-bis(pentafluorophenyl)-o-phenylenediamide] with the pre-activation of a-alkyl-substituted adiazoesters reagents by LiAl(OR F ) 4 [OR F = (OC(CF 3 ) 3 ]p rovides unprecedented access to selective iron-catalyzed intramolecular functionalization of strong alkyl C(sp 3 ) À Hb onds. Reactions occur at 25 8 8Cvia a-alkyl-metallocarbene intermediates,a nd with activity/selectivity levels similar to those of rhodium carboxylate catalysts.M echanistic investigations reveal ac rucial role of the lithium cation in the ratedetermining formation of the electrophilic iron-carbene intermediate,w hich then proceeds by concerted insertion into the C À Hb ond.Scheme 1. State of art of iron-carbene-mediatedC (sp 3 )ÀHfunctionalization.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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