Unveiling N-Fused Nitreniums as Potent Catalytic Photooxidants

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 3603 - 3608

Опубликована: Янв. 31, 2024

The first example of a hitherto-unknown facet catalytic photooxidant capability nitrenium cations is reported herein. fundamental limitation inability the traditional and nitreniums to achieve excited-state redox potential beyond +2.0 V (vs Ag/AgCl), primary requirement for powerful photooxidant, addressed in this work by developing structurally unique class N-fused cations, with required structural engineering involving extensive π-conjugation through ring fusion at site, which enabled significant lowering LUMO energy easy reduction excited state (excited-state up +2.5 vs facilitated effective delocalization/stabilization generated radical. This finding opens new way discover novel useful (photo)catalytic properties just Lewis acidity.

Язык: Английский

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Additive free, N-heterocyclic nitrenium catalyzed photoreduction of cycloketone oxime esters

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1160 - 1165

Опубликована: Янв. 1, 2023

N-Heterocyclic nitrenium iodide salts can be used as ideal charge transfer complex catalysts for the photoreduction of cycloketone oxime esters.

Язык: Английский

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N-Heterocyclic Nitrenium-Catalyzed Photohomolysis of CF₃SO₂Cl for Alkene Trifluoromethylation

Organic Letters, Год журнала: 2023, Номер 25(33), С. 6189 - 6194

Опубликована: Авг. 14, 2023

N-Heterocyclic nitreniums (NHNs) have been utilized as Lewis acid catalysts to activate substrates with lone pairs. Alternative their conventional applications, we discovered that NHNs can also serve charge transfer complex catalysts. Herein, present another potential of by utilizing a weak interaction between and CF3SO2Cl. The method promotes CF3SO2Cl undergo photohomolysis, resulting in the CF3 radical. Mechanistic studies suggested could be due π-hole effect NHNs.

Язык: Английский

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Multimodal Reactivity of N–H Bonds in Triazanes and Isolation of a Triazinyl Radical

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(51), С. 23642 - 23648

Опубликована: Дек. 16, 2022

The employment of nitrogen Lewis acids based on nitrenium cations has been increasingly featured in the fields main group chemistry and catalysis. A formally reduced form D─cyclic triazanes E─are intriguing chemical compounds, which is completely unexplored. In this work, we reveal that N–H-triazanes exhibit unusual N–H bond properties; namely, they can serve as protons, hydrides, or hydrogen atom donors. This unique multimodal reactivity provides an N-cation, N-anion, N-radical from same species. It allowed us to isolate, for first time, a stable naphto[1,2,3]triazinyl radical, was fully characterized both computationally experimentally, including its monomeric X-ray structure. Moreover, radical be prepared directly cation by single electron reduction (E = −0.46 V), process reversible. We envision versatile uses synthetic materials chemistry.

Язык: Английский

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Photoinduced N-heterocyclic nitrenium-catalyzed single electron reduction of Se–Se bond for the generation of nucleophilic selenolates

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(7), С. 2070 - 2074

Опубликована: Янв. 1, 2024

A straightforward photoinduced NHN-catalyzed method for generating nucleophilic selenolates from diselenides without the need of stoichiometric reductants.

Язык: Английский

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Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

The ligated boryl radical (LBR) has emerged as a potent tool for activating alkyl halides in transformations through halogen-atom transfer (XAT). However, unactivated chlorides still present an open challenge this strategy. We herein describe new activation mode of the LBR to construct C(sp

Язык: Английский

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N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization

Green Synthesis and Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Март 1, 2024

The photoredox radical-polar crossover paradigm is a valuable tool for 1,2-difunctionalization of alkenes. However, the use unactivated alkyl halides as radical precursors remains far less developed. Here, we report photoreductive N-heterocyclic nitrenium-catalyzed 1,2-dicarbofunctionalization alkenes by using and aryl iodides. These reactions can be carried out under simple, transition-metal-free conditions with easily obtainable materials such alkyl/aryl halides, alkenes, aldehydes. exhibit broad range substrate compatibility good tolerance towards functional groups. This approach offers new to unlock carbon skeletons.

Язык: Английский

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Triazenolysis of alkenes as an aza version of ozonolysis

Nature Chemistry, Год журнала: 2024, Номер 17(1), С. 101 - 110

Опубликована: Окт. 11, 2024

Язык: Английский

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Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis

Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Сен. 19, 2024

Abstract N-Heterocyclic nitreniums (NHNs) are isoelectronic and isostructural analogues of N-heterocyclic carbenes (NHCs). Unlike NHCs, NHNs much less developed. While a comprehensive understanding NHN reactivity remains elusive, recent advancements have demonstrated their utility as Lewis acid catalysts, photoreductants, photooxidants, leading to several reaction patterns. In this short review, we focus on the applications in photoredox reactions. We also discuss mechanisms behind these transformations outline future research directions. 1 Introduction 2 Application Nitreniums Photoreductants 3 Facilitate Photohomolysis 4 Photooxidants 5 Conclusion

Язык: Английский

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Exploring the Electronic Properties of Cyclic Five-Membered 1,2,3-Triazolium Ions: A Quantum Chemical Study

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Май 17, 2025

Cyclic nitrenium ions (CNIs) are generally stable and have found applications in chemistry, including biochemistry. five-membered 1,2,3-triazolium (CFTIs) a special class of CNIs; such moieties few medicinally important species. Though they isoelectronic to N-heterocyclic carbenes (NHCs), exhibit electrophilic properties (unlike nucleophilic NHCs). A quantum chemical studies were reported, but extensive study on CFTIs is required understand their electronic features design species with tailored properties. In this work, thorough analysis has been carried out the standard CFTI (1,3-dimethyl-1,2,3-triazolium ion). Hydride ion affinity fluoride parameters estimated evaluate Lewis acidic character CFTIs. Also, electrophilicity these terms global index (ω) values. The complexation energies PMe3 (ΔHPMe3) 1,3-dimethylimidazol-2-ylidene (ΔHNHC) also estimated. modulation as function substitution ring fusion evaluated. correlation between ΔHPMe3 ΔHNHC very high (R = 0.99); helps identifying that may character.

Язык: Английский

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