Photoinduced Hydrodifluoromethylation and Hydromethylation of Alkenes Enabled by Ligand-to-Iron Charge Transfer Mediated Decarboxylation

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1300 - 1310

Опубликована: Янв. 11, 2024

Directly utilizing abundant and inexpensive sources of aliphatic carboxylic acids is highly attractive for the synthesis CF2H- CH3-containing compounds. Herein, we report a versatile photoinduced iron-catalyzed platform hydrodifluoromethylation hydromethylation alkenes without need additional stoichiometric oxidants. These two transformations are accomplished by visible-light-induced ligand-to-iron charge transfer open-shell activation system using industrial chemical difluoroacetic acetic as precursors postulated to operate via difluoromethyl methyl radical-mediated decarboxylation mechanism. Experimental results show that strategy also applicable difunctionalization unactivated alkenes. Meanwhile, this provides viable route pharmaceutically active molecules containing deuterated units. The protocol exhibits several features, including mild reaction conditions, divergent radical precursors, operational simplicity scalability, good chemo- regioselectivity, scalability supported continuous flow technology, ability provide high-value building blocks applications in one step.

Язык: Английский

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Photo‐ and Cobalt‐Catalyzed Synthesis of Heterocycles via Cycloisomerization of Unactivated Olefins

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Фев. 28, 2024

Abstract We report a general, intramolecular cycloisomerization of unactivated olefins with pendant nucleophiles. The reaction proceeds under mild conditions and tolerates ethers, esters, protected amines, acetals, pyrazoles, carbamates, arenes. It is amenable to N ‐, O as well C ‐nucleophiles, yielding number different heterocycles including, but not limited to, pyrrolidines, piperidines, oxazolidinones, lactones. Use both benzothiazinoquinoxaline organophotocatalyst Co‐salen catalyst obviates the need for stoichiometric oxidant or reductant. showcase utility protocol in late‐stage drug diversification synthesis several small natural products.

Язык: Английский

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Iron-Catalyzed Aerobic Carbonylation of Methane via Ligand-to-Metal Charge Transfer Excitation

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 6, 2025

The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization inert C-H bonds, facilitating use nonprecious metal catalysts in demanding transformations. Notably, aerobic carbonylation methane to acetic acid remains formidable due rapid oxidation methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT achieve exceptional C2/C1 selectivity through synergistic photoexcitation, generation, and carbonylation. Mechanistic studies highlight critical roles Fe(II) Fe-carbonyl complexes bypassing via a rebound-like pathway, unlocking unprecedented efficiency

Язык: Английский

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Radical-Mediated Decarboxylative C–C and C–S Couplings of Carboxylic Acids via Iron Photocatalysis

Organic Letters, Год журнала: 2024, Номер 26(5), С. 1110 - 1115

Опубликована: Янв. 26, 2024

Despite the significant success of decarboxylative radical reactions, catalytic systems vary considerably upon different acceptors, requiring renewed case-by-case reaction optimization. Herein, we developed an iron condition that enables highly efficient decarboxylation various carboxylic acids for a range transformations. This operationally simple protocol was amenable to wide array delivering structurally diverse oxime ethers, alkenylation, alkynylation, thiolation, and amidation products in useful excellent yields (>40 examples, up 95% yield).

Язык: Английский

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Selective Arene Photonitration via Iron-Complex β-Homolysis

JACS Au, Год журнала: 2024, Номер 4(12), С. 4899 - 4909

Опубликована: Ноя. 21, 2024

Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields pharmaceuticals, dyes, pesticides, functional materials, fertilizers, explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge fumes waste acids, poor group tolerance, tremendous purification difficulty, renders mild, efficient, environmentally friendly a formidable challenge. Herein, we develop visible-light-driven biocompatible arene C–H strategy with good efficiency regioselectivity, marvelous substrate applicability wide application scale-up synthesis, total late-stage functionalization. A nitryl radical delivered through unusual β-homolysis photoexcited ferric-nitrate complex proposed to be key nitrification reagent this system.

Язык: Английский

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Regio- and Enantioselective Nickel-Catalyzed Ipso- and Remote Hydroamination Utilizing Organic Azides as Amino Sources for the Synthesis of Primary Amines

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

Опубликована: Окт. 23, 2024

Primary amines serve as key synthetic precursors to most other

Язык: Английский

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Visible-light induced selenocyclization of 2-ethynylanilines under ambient conditions: simple FeBr3 as a dual-functional catalyst

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(30), С. 6198 - 6204

Опубликована: Янв. 1, 2024

Reported herein is a visible-light induced selenocyclization of 2-ethynylanilines under ambient conditions, with simple FeBr 3 as dual-functional catalyst.

Язык: Английский

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N-Protonated Acridinium Catalyst Enables Anti-Markovnikov Hydration of Unconjugated Tri- and Disubstituted Olefins

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(6), С. 4736 - 4742

Опубликована: Янв. 31, 2025

The preparation of alcohols with anti-Markovnikov selectivity directly from olefins and water is a sought-after reaction due to its atom-economy potential cost-effectiveness. Herein, we present the first general method for direct, catalytic hydration unconjugated tri- disubstituted olefins. key advancement made possible by an oxidative (E*red = 2.15 V) N-H acridinium catalyst, which allowed functionalization alkenes that were previously unreactive in such transformations their high oxidation potential. developed protocol not limited but also enables other hydrofunctionalizations, as hydroetherifications, following same mechanistic pathway.

Язык: Английский

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Ligand Influence on the Performance of Cesium Lead Bromide Perovskite Quantum Dots in Photocatalytic C(sp³)–H Bromination Reactions

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Lead halide perovskite quantum dots (LHP QDs) CsPbX3 generate immense interest as narrow-band emitters for displays, lasers, and light sources. All QD applications rely on suited engineering of surface capping ligands. The first generation LHP QDs employed oleic acid/oleyl amine have found only a limited use in photoredox catalysis. These catalysts been reported to be unstable decompose over the course reaction, thus reducing turnover numbers (TONs) limiting their synthetic ability. Herein, impact eight distinct ligands monodisperse CsPbBr3 is reported, affording thorough comprehension performance photocatalytic C–H brominations. efforts yielded operating at extremely low catalyst loadings (<100 ppb) with TONs 9,000,000 per QD. We emphasize that optimal catalytic requires increased accessibility without compromising structural colloidal integrity. Control experiments indicated well-known such Ir(ppy)3, Ru(bpy)3Cl2, or 4CzlPN are ineffective same reaction. Mechanistic studies reveal C–Br bond reduction CH2Br2 rate-limiting step likely facilitated through interaction surface. This work outlines holistic approach toward design practically useful photocatalysts out comprising structurally soft cores dynamically bound

Язык: Английский

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Oxidative amination by nitrogen atom insertion into carbon-carbon double bonds

Science, Год журнала: 2025, Номер 387(6738), С. 1108 - 1114

Опубликована: Март 6, 2025

The synthesis of nitrogen-containing molecules through carbon-nitrogen (C-N) bond formation is critical for the discovery and preparation medicines, agrochemicals, materials. Here, we report direct insertion a nitrogen atom into unactivated carbon-carbon double bonds to access aza-allenium intermediates, which can be converted either nitriles or amidine products, depending on initial alkene substitution pattern. This operationally simple highly functionally compatible reaction works wide range alkenes. PIFA, commercially available inexpensive hypervalent iodine reagent, key this reactivity. Our mechanistic proposal supported by chemical trapping experiments, concomitantly demonstrate utility our method valuable N-heterocycles. Additionally, used as general strategy synthesizing amides amines, well 15N-labeled molecules.

Язык: Английский

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