
Research Square (Research Square), Год журнала: 2023, Номер unknown
Опубликована: Окт. 30, 2023
Язык: Английский
Research Square (Research Square), Год журнала: 2023, Номер unknown
Опубликована: Окт. 30, 2023
Язык: Английский
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
Процитировано
11Journal of the American Chemical Society, Год журнала: 2023, Номер 145(22), С. 12214 - 12223
Опубликована: Май 24, 2023
Simple aromatic compounds like benzene are abundant feedstocks, for which the preparation of derivatives chiefly begins with electrophilic substitution reactions or, less frequently, reductions. Their high stability makes them particularly reluctant to participate in cycloadditions under ordinary reaction conditions. Here, we demonstrate exceptional ability 1,3-diaza-2-azoniaallene cations undergo formal (3 + 2) unactivated below room temperature, providing thermally stable dearomatized adducts on a multi-gram scale. The cycloaddition, tolerates polar functional groups, activates ring toward further elaboration. On treatment dienophiles, cycloadducts (4 cycloaddition–cycloreversion cascade yield substituted or fused arenes, including naphthalene derivatives. overall sequence results transmutation arenes through an exchange carbons: two-carbon fragment from original is replaced another incoming dienophile, introducing unconventional disconnection synthesis ubiquitous building blocks. Applications this two-step acenes, isotopically labeled molecules, and medicinally relevant demonstrated.
Язык: Английский
Процитировано
18Organic 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
Процитировано
16Organic 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
Процитировано
14Organic Letters, Год журнала: 2022, Номер 24(33), С. 6105 - 6110
Опубликована: Авг. 16, 2022
In this work, benzotriazolium salts have been introduced as efficient, readily accessible, bench-stable Lewis acid catalysts. Though these sorts of N-heterocyclic compounds found wide applications ionic liquids or electrolytes, their catalytic activity remained unexplored. Herein, potential catalysts was demonstrated in two prototypical allylic and Nazarov cyclization reactions, showing a matching reactivity allowing low loadings (down to 0.5 mol %).
Язык: Английский
Процитировано
22Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(5), С. 932 - 939
Опубликована: Янв. 1, 2024
A rapid and mild protocol for the exhaustive deoxygenation of various aromatic ketones to corresponding alkanes using AB as a reductant TiCl 4 catalyst.
Язык: Английский
Процитировано
5Journal 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
Процитировано
17Organic 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
Процитировано
4Green 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
Процитировано
3Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19474 - 19488
Опубликована: Июль 4, 2024
Amid the escalating integration of renewable energy sources, demand for grid storage solutions, including non-aqueous organic redox flow batteries (oRFBs), has become ever more pronounced. oRFBs face a primary challenge irreversible capacity loss attributed to crossover redox-active materials between half-cells. A possible solution involves utilization bipolar electrolytes that act as both catholyte and anolyte. Identifying such molecules poses several challenges it requires delicate balance stability oxidation states density, which is influenced by separation two events. We report development diaminotriazolium core capable producing electronically distinct persistent radical species with typically extreme reduction potentials (
Язык: Английский
Процитировано
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