Iron porphyrin-catalysed C(sp<sup>3</sup>)–H amination with alkyl azides for the synthesis of complex nitrogen-containing compounds

Fan, Jintu; Wang, Ye; Hu, Xuefu; Liu, Yungen; Che, Chi‐Ming

doi:10.1039/d2qo01972h

Cited by 7 publications

(2 citation statements)

References 81 publications

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“…Other examples are related to the processes of the CÀ N bond formation catalyzed by iron or ruthenium containing compounds, e. g. [48,49] Theoretical studies on methane hydroxylation reaction with presence of aromatic cyclic compounds containing Ru or Fe were performed by Sharma et al [50] Another example is experimental and theoretical study of the reactivity patterns and reaction mechanisms in e. g. alkane hydroxylation catalyzed by a mononuclear nonheme ruthenium(IV)-oxo com-plex, [Ru IV (O)(terpy)(bpm)] 2 + . [51] It was showed that in the alkane hydroxylation process, the experimental and theoretical results revealed that the dissociation of the substrate radical formed via a rate-determining hydrogen atom abstraction of an alkane C À H bond is more favorable energetically than other processes.…”

Section: Introductionmentioning

confidence: 99%

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Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Kizior,

Jezierska,

Szyja

2023

ChemPhysChem

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The partial oxidation reaction of CH4 led to the formation of CH3OH in the presence of Ru‐porphyrin oxo complexes (denoted as POR, POR‐O and POR‐OH where in the case of the last two, oxygen atom and the OH group were attached to the active site, respectively), in which Ru was present on different oxidation states. The simulations were performed based on Density Functional Theory (DFT) with extended geometric and electronic structure analyses of each reaction step. Moreover, the reaction pathways were investigated in different spin states. The Spin Crossover (SCO) phenomenon was found to play an important role in the kinetics of the reaction in the presence of POR and POR‐O. Harmonic Oscillator Model of Aromaticity (HOMA) index was applied for different spin states to estimate the aromaticity changes of the pyrrole rings in the Ru‐porphyrin complexes. In order to characterize the nature of bonding, the Natural Bond Orbitals (NBO) analysis including the Wiberg Bond Index (WBI) and Natural Population Analysis (NPA) was carried out. Finally, the Non‐Covalent Interactions (NCI) index was employed to gain insight into interactions between the components of the reaction. It was found that the non‐covalent interactions cannot be neglected in the studied reaction paths.

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Section: Introductionmentioning

confidence: 99%

“…Other examples are related to the processes of the C−N bond formation catalyzed by iron or ruthenium containing compounds, e. g [48,49] . Theoretical studies on methane hydroxylation reaction with presence of aromatic cyclic compounds containing Ru or Fe were performed by Sharma et al [50] .…”

Section: Introductionmentioning

confidence: 99%

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Kizior,

Jezierska,

Szyja

2023

ChemPhysChem

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Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

You,

Shing,

et al. 2024

Advanced Science

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As nitrogen analogues of iron‐oxo species, high‐valent iron‐imido species have attracted great interest in the past decades. FeV‐alkylimido species are generally considered to be key reaction intermediates in Fe(III)‐catalyzed C(sp3)─H bond aminations of alkyl azides but remain underexplored. Here, it is reported that iron‐corrole (Cor) complexes can catalyze a wide range of intramolecular C─H amination reactions of alkyl azides to afford a variety of 5‐, 6‐ and 7‐membered N‐heterocycles, including alkaloids and natural product derivatives, with up to 3880 turnover numbers (TONs) and excellent diastereoselectivity (>99:1 d.r.). Mechanistic studies including density functional theory (DFT) calculations and intermolecular hydrogen atom abstraction (HAA) reactions reveal key reactive FeV‐alkylimido intermediates. The [FeV(Cor)(NAd)] (Ad = adamantyl) complex is independently prepared and characterized through electron paramagnetic resonance (EPR), resonance Raman (rR) measurement, and X‐ray photoelectron spectroscopy (XPS). This complex is reactive toward HAA reactions with kinetic isotope effects (KIEs) similar to [Fe(Cor)]‐catalyzed intramolecular C─H amination of alkyl azides.

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Homogeneous Iron Catalyzed C−H Amination

Possenti,

Olivo

2024

ChemCatChem

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Iron‐catalyzed C—H amination is emerging as an attractive and sustainable method to install amine functionalities into organic compounds. Amination of C(sp3)—H bonds is usually mediated by an iron‐nitrene intermediate via a Hydrogen Atom Abstraction/Radical Recombination mechanism reminiscent of biomimetic C—H oxidation. Accordingly, this transformation can be catalyzed by engineered iron enzymes, heme and nonheme iron complexes as well as iron salts, although it is often limited to intramolecular reactions and/or activated positions. Aromatic C(sp2)—H amination is mediated by addition of electrophilic iron nitrenes or protonated N‐radical intermediates (produced with Fe catalysts) to aromatic systems. Again, high selectivity is obtained via (pseudo) intramolecular reactions. From a mechanistic perspective, several iron nitrene intermediates have been isolated and characterized over the years in different ligand scaffolds and iron oxidation states. Structure‐activity correlations have been drawn only in few cases and point to a key role of the spin density on the nitrene ligand and of the iron oxidation state. This review describes the state of the art for homogeneous iron catalyzed C(sp3)—H and C(sp2)—H amination focusing on the last 5 years (2019‐2023) from a mechanism‐driven catalyst design perspective.

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Iron porphyrin-catalysed C(sp³)–H amination with alkyl azides for the synthesis of complex nitrogen-containing compounds

Abstract: With the readily prepared iron porphyrin complex as a catalyst and starting with alkyl azides, a panel of nitrogen-containing skeletons representing the families of natural alkaloids and bioactive compounds could be prepared in good yields.

Cited by 7 publications

References 81 publications

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

Homogeneous Iron Catalyzed C−H Amination

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Iron porphyrin-catalysed C(sp3)–H amination with alkyl azides for the synthesis of complex nitrogen-containing compounds

Abstract: With the readily prepared iron porphyrin complex as a catalyst and starting with alkyl azides, a panel of nitrogen-containing skeletons representing the families of natural alkaloids and bioactive compounds could be prepared in good yields.

Cited by 7 publications

References 81 publications

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Partial Methane Oxidation to Methanol on Ru‐Porphyrins – on the Role of Non‐Innocent Ligands and Spin Crossover

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [FeV(Cor)(NAd)]

Homogeneous Iron Catalyzed C−H Amination

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Product

Resources

About

Iron porphyrin-catalysed C(sp³)–H amination with alkyl azides for the synthesis of complex nitrogen-containing compounds

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]