Interweaving Visible‐Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones

Abstract

Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp 3 )-N, N = S, and N = Pb ond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions.I n contrast to intramolecular CÀHa midations strategies,a n intermolecular regioselective CÀHa midation via visiblelight-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via ar adical pathway.C omputational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.Scheme 1. Transition-metal-catalyzedn itrene formation and transformation with dioxazolones.

Iron‐Catalyzed Intramolecular Arene C(sp2)−H Amidations under Mechanochemical Conditions

“…Due to experimental challenges of analyzing the reaction progress under mechanochemical conditions, several steps have to remain descriptive at this stage. In analogy to the discussion by Bao, Yu, and co‐workers for reactions (in solution) with a 3‐phenyl substituted dioxazolone and FeCl 3 , [20b] we propose an activation of substrate 1 by coordination of FeBr 3 . Loss of CO 2 leads to a new species A , formally corresponding to an acylnitrene iron intermediate [21] .…”

Visible-Light-Induced Iron Group Metal Catalysis: Recent Developments in Organic Synthesis

“…In 2021, Bao and co-workers reported a protocol of ironcatalyzed nitrene transfer reaction with dioxazolones for the intermolecular C-N, N=S, and N=P bond formation under visible-light irradiation (Scheme 9). 16 The optical absorption studies revealed that the initial formation of a photoactive iron species coordinated with dioxazolone. Through a computational study, the reaction was proved to be exothermic and the spin state of the Fe/N species was found to keep in the sextet state.…”

Recent Advances in Decarboxylative Conversions of Cyclic Carbonates and Beyond

“…Bao and co-workers disclosed an efficient and practical protocol for the intermolecular construction of C-N, N=S and N=P bonds via a Fe-catalyzed nitrene-transfer strategy from dioxazolones, which was driven by visible-light irradi-ation without the addition of an extra photosensitizer (Scheme 27). 45 A wide range of functional groups was tolerated under mild conditions. Control experiments support the fact that the reactions proceed through a radical pathway.…”