A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids DOI Creative Commons
Luca Mareen Denkler,

Meghana Aladahalli Shekar,

Tak Shing Jason Ngan

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(32)

Опубликована: Май 13, 2024

Abstract We report an iron‐catalyzed decarboxylative C(sp 3 )−O bond‐forming reaction under mild, base‐free conditions with visible light irradiation. The transformation uses readily available and structurally diverse carboxylic acids, iron photocatalyst, 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) derivatives as oxygenation reagents. process exhibits a broad scope in acids possessing wide range of stereoelectronic properties functional groups. developed was applied to late‐stage series bio‐active molecules. leverages the ability complexes generate carbon‐centered radicals directly from by photoinduced carboxylate‐to‐iron charge transfer. Kinetic, electrochemical, EPR, UV/Vis, HRMS, DFT studies revealed that TEMPO has triple role reaction: reagent, oxidant turn over Fe‐catalyst, internal base for acid deprotonation. obtained adducts represent versatile synthetic intermediates were further engaged C−C C‐heteroatom reactions using commercial organo‐photocatalysts nucleophilic

Язык: Английский

Photocatalytic hydrofluoroalkylation of alkenes with carboxylic acids DOI

Kang‐Jie Bian,

Yen‐Chu Lu, David Nemoto

и другие.

Nature Chemistry, Год журнала: 2023, Номер 15(12), С. 1683 - 1692

Опубликована: Ноя. 13, 2023

Язык: Английский

Процитировано

77

A new era of LMCT: leveraging ligand-to-metal charge transfer excited states for photochemical reactions DOI Creative Commons
Ann M. May, Jillian L. Dempsey

Chemical Science, Год журнала: 2024, Номер 15(18), С. 6661 - 6678

Опубликована: Янв. 1, 2024

Ligand-to-metal charge transfer (LMCT) excited states showcase promise in enabling photochemical reactions. This article details design principles to enable low energy LMCT and notable examples that drive reactions from these states.

Язык: Английский

Процитировано

54

Direct Decarboxylation of Trifluoroacetates Enabled by Iron Photocatalysis** DOI Creative Commons
Sara Fernández‐García, Veronika O. Chantzakou, Francisco Juliá‐Hernández

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 13, 2023

Trifluoroacetates are the most abundant and accessible sources of trifluoromethyl groups, which key components in pharmaceuticals agrochemicals. The generation reactive radicals from trifluoroacetates requires their decarboxylation, is hampered by high oxidation potential. This constitutes a major challenge for redox-based methods, because need to pair redox potentials with trifluoroacetate. Here we report strategy based on iron photocatalysis promote direct photodecarboxylation that displays reactivity features escape limitations. Our synthetic design has enabled use trifluoromethylation more easily oxidizable organic substrates, offering new opportunities late-stage derivatization campaigns using chemical feedstocks, Earth-abundant catalysts, visible-light.

Язык: Английский

Процитировано

51

An iron-catalyzed C–S bond-forming reaction of carboxylic acids and hydrocarbons via photo-induced ligand to metal charge transfer DOI

Ao-Men Hu,

Jia‐Lin Tu,

Mengqi Luo

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(19), С. 4764 - 4773

Опубликована: Янв. 1, 2023

A photo-induced iron-catalyzed strategy that facilitates the transformation of carboxylic acids and hydrocarbons into thioethers sulfoxides is herein reported.

Язык: Английский

Процитировано

31

The great strides of iron photosensitizers for contemporary organic photoredox catalysis: On our way to the holy grail? DOI
Felix Glaser,

Akin Aydogan,

Benjamin Elias

и другие.

Coordination Chemistry Reviews, Год журнала: 2023, Номер 500, С. 215522 - 215522

Опубликована: Ноя. 9, 2023

Язык: Английский

Процитировано

27

Photocatalytic, modular difunctionalization of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer DOI Creative Commons

Kang‐Jie Bian,

David Nemoto, Xiaowei Chen

и другие.

Chemical Science, Год журнала: 2023, Номер 15(1), С. 124 - 133

Опубликована: Ноя. 24, 2023

Simple iron salts are able to photocatalyze the diazidation, dichlorination, and fluorochlorination of alkenes via merger ligand-to-metal charge transfer (LMCT) either radical ligand (RLT) or fluorine atom (FAT).

Язык: Английский

Процитировано

27

Radical Phosphorylation of Aliphatic C–H Bonds via Iron Photocatalysis DOI

Guang-Da Xia,

Zi‐Kui Liu,

Yulian Zhao

и другие.

Organic Letters, Год журнала: 2023, Номер 25(28), С. 5279 - 5284

Опубликована: Июль 11, 2023

The synthesis of tertiary phosphines(III) has been a long-standing challenge in synthetic chemistry because inevitable issues including harsh conditions, sensitive organometallic reagents, and prefunctionalized substrates traditional synthesis. Herein, we report strategically novel C(sp3)-H bond phosphorylation that enables the assembly structurally diverse from industrial phosphine(III) sources under mild photocatalytic conditions. merger ligand-to-metal charge transfer (LMCT) FeCl3 with hydrogen atom-transfer (HAT) process is key for generation alkyl radicals hydrocarbons. Strikingly, this catalytic system can be successfully applied polymerization electron-deficient alkenes.

Язык: Английский

Процитировано

24

Radical-Mediated Decarboxylative C–C and C–S Couplings of Carboxylic Acids via Iron Photocatalysis DOI
Lijing Li, Wei Yi,

Yulian Zhao

и другие.

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

Процитировано

16

Decarboxylative Sulfonylation of Carboxylic Acids under Mild Photomediated Iron Catalysis DOI

Yuanqi Dong,

Ni Xiong,

Zhouting Rong

и другие.

Organic Letters, Год журнала: 2024, Номер 26(12), С. 2381 - 2386

Опубликована: Март 15, 2024

Organic sulfones are an important class of chemical compounds widely used in many research fields. The direct decarboxylative sulfonylation carboxylic acids is attractive but challenging, particularly when iron as a metal catalyst. Herein, we describe photoinduced iron-catalytic method for the synthesis directly using via radical-based decarboxylation. This protocol mild, highly efficient, and easy-to-operate. A broad scope carbon electrophiles could be well tolerated. mechanism involving iron-catalyzed decarboxylation, radical transfer, single-electron reduction, nucleophilic attack proposed.

Язык: Английский

Процитировано

15

Iron photocatalysis via Brønsted acid-unlocked ligand-to-metal charge transfer DOI Creative Commons
Xiaoyu Jiang, Yu Lan,

Yudong Hao

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 20, 2024

Abstract Reforming sustainable 3d-metal-based visible light catalytic platforms for inert bulk chemical activation is highly desirable. Herein, we demonstrate the use of a Brønsted acid to unlock robust and practical iron ligand-to-metal charge transfer (LMCT) photocatalysis multifarious haloalkylcarboxylates (C n X m COO − , = F or Cl) produce C radicals. This process enables fluoro-polyhaloalkylation non-activated alkenes by combining easily available Selectfluor as fluorine source. Valuable alkyl fluorides including potential drug molecules can be obtained through this protocol. Mechanistic studies indicate that real light-harvesting species may derive from in situ-assembly Fe 3+ H + acetonitrile solvent, which indeed increases efficiency LMCT between center via hydrogen-bond interactions. We anticipate acid-unlocked platform would an intriguing option execute compounds.

Язык: Английский

Процитировано

15