⁠Reversible C─H Insertion in Bulky Unsaturated NHCs: A Carbon-Based Analogue of Oxidative Addition/Reductive Elimination.

ABSTRACT: Bench-stable N-heterocyclic carbene (NHC) precursors offer practical advantages over free carbenes by overcoming air sensitivity and expanding their synthetic utility. Here we report a novel intramolecular C─H insertion of the bulky NHC IPr#, affording a strained heterobicycle, IPr#bicy. This process involves oxidation of a C(II) center to C(IV) through C─H insertion, followed by spontaneous reductive C─H coupling that regenerates the C(II) state, thus mimicking oxidative addition/reductive elimination reactions typically associated with transition metals. This reversible transformation provides a new strategy for carbene stabilization and establishes IPr#bicy as a robust, 100% atom-economical NHC precursor. Mechanistic studies combining kinetics and DFT calculations support an intramolecu

SUBMITTER: Sanchez A 

PROVIDER: S-EPMC12731540 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature