Atomically Dispersed Co-N/C Catalyst for Divergent Synthesis of Nitrogen-Containing Compounds from Alkenes

Abstract

Alkene functionalization with a single-atom catalyst (SAC) which merges homogeneous and heterogeneous catalysis is a fascinating route to obtain high-value-added molecules. However, C–N bond formation of alkene with SAC is still unexplored. Herein, a bimetal-organic framework-derived Co–N/C catalyst with an atomically dispersed cobalt center is reported to show good activity of chemoselective aziridination/oxyamination reactions from alkene and hydroxylamine, and late-stage functionalization of complex alkenes and diversified synthetic transformations of the aziridine product further expand the utility of this method. Moreover, this system proceeds without external oxidants and exhibits mild, atom-economic, and recyclable characters. Detailed spectroscopic characterizations and mechanistic studies revealed the structure of the catalytic center and possible intermediates involved in the mechanism cycle.

Direct C−C Double Bond Cleavage of Alkenes Enabled by Highly Dispersed Cobalt Catalyst and Hydroxylamine

“…In sharp contrast, these hydroxylamines, except for O-(2,4dinitrophenyl)hydroxylamine, were infeasible for the Co SA -N/C catalyzed alkene aziridination and oxyamination. [15] Figure 1. Synthesis of single-atom cobalt catalyst.…”

“…Another major difference was the previous report was mainly effective for terminal alkenes, [15] while this cleavage reaction required internal alkenes in most cases.…”

Recent advances in the accessibility, synthetic utility, and biological applications of aziridines

“…Several natural products and drug-derived olefins have also been subjected to aziridination. 28 Díez-González and co-workers reported the preparation of aziridines ( 82) from readily available azides (80) and alkenes (81). The reaction was carried out without any further additive by using technical solvents without the need for an inert atmosphere as the reaction can proceed in reaction vessels open to air (Scheme 16).…”

Single‐Atom Catalysis in Organic Synthesis

“…Finally, Tang et al showcased an example of a singleatom catalyst for the CÀ N bond formation between alkenes and hydroxylamine (Scheme 30). [66] The catalyst allowed for aziridines and oxyamination products to be obtained in 25-60 % isolated yields. The protocol was also tested in latestage functionalization of complex alkenes, obtaining pharmaceutically useful derivatives from common scaffolds, like coumarin, fenofibrate, and tyroxine.…”