Copper and Iron Make the Difference: Developing Sustainable Photoredox Catalyzed Transformations DOI
Oliver Reiser

Published: July 22, 2024

Synthetic organic chemistry undertakes significant efforts to develop new catalytic transformations that utilize greener reagents and avoid stoichiometric additives. In this regard, visible-light photoredox catalysis offers a unique activation mode of molecules, which serves as an alternative many thermal transition-metals catalyzed reactions. Most photoredox-catalyzed processes capitalize on heavy metals, namely, Ru(II) or Ir(III)-complexes, can serve single electron oxidants reductants in their photoexcited states. Copper-and iron-based photo¬catalysts are rapidly emerging, offering economic ecologic advantages but, addition, interact with substrates beyond transfer via inner sphere mechanisms, have been successfully utilized achieve challenging transformations. Emphasizing the principles catalysis, selected synthetic applications from our laboratory will be discussed, highlighting opportunities copper- iron-photocatalysts offer area.

Language: Английский

Selective Arene Photonitration via Iron-Complex β-Homolysis DOI Creative Commons

Shuyang Liu,

Ziyu Gan, Min Jiang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(12), P. 4899 - 4909

Published: Nov. 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.

Language: Английский

Citations

6
Synthesis of Acylbenzo[b]thiophenes, Benzofurans and Indoles via Intramolecular Oxidative Cyclization Enabled by Photocatalytic Hydrogen Atom Transfer (HAT) DOI Creative Commons

Fen-Dou Wang,

Jin Jiang,

Tiantian Xu

et al.

Tetrahedron Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100119 - 100119

Published: Jan. 1, 2025

An efficient strategy for intramolecular oxidative cyclization of 2-alkynylthioanisoles toward 3-acylbenzo[b]thiophenes by photochemical hydrogen atom transfer catalysis has been developed. 3-Acylbenzo[b]selenophenes, benzofurans and indoles can also be prepared this protocol. This reaction is convenient to perform at room temperature under simple conditions using air as the oxidant. Mechanistic studies revealed that formation α-thioalkyl radicals intermediate crucial.Graphical abstract

Language: Английский

Citations

0
Wavelength-Selective Reactivity of Iron(III) Halide Salts in Photocatalytic C–H Functionalization DOI Creative Commons

Cory T. Ludwig,

Isiaka Owolabi,

L Evans

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 24, 2025

The utility of halogen radicals in hydrocarbon functionalization extends from early examples photochemical halogenation to recent reports using photoredox catalysis with iridium complexes and simple transition metal salts such as FeCl3. majority these methods (uncatalyzed iron-catalyzed) require UV light (λ ≤ 390 nm), systematic efforts enable the use visible remain valuable. We report a Fe(III) salt that enables C–H C–C C–N under light. reactivity selectivity profile different sources demonstrates wavelength-selective behavior, which was further investigated deuterium kinetic isotope effect experiments DFT calculations. These results show control over reactive intermediates this iron-catalyzed reaction can be achieved through proper choice wavelength irradiation.

Language: Английский

Citations

0
Trendbericht Photochemie 2025 DOI
Thorsten Bach, Alexander Breder, Tanja Gulder

et al.

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(4), P. 56 - 67

Published: March 31, 2025

Abstract Dieser Trendbericht erläutert Erkenntnisse der letzten beiden Jahre aus Sicht von Wissenschaftlerinnen und Wissenschaftlern des interdisziplinären, durch die DFG geförderten Konsortiums Transregio 325. Die Autorinnen Autoren forschen vor allem zu chemischer Photokatalyse beleuchten besonders Themen mit molekülchemischer Komponente.

Citations

0
Copper and Iron Make the Difference: Developing Sustainable Photoredox Catalyzed Transformations DOI
Oliver Reiser

Published: July 22, 2024

Synthetic organic chemistry undertakes significant efforts to develop new catalytic transformations that utilize greener reagents and avoid stoichiometric additives. In this regard, visible-light photoredox catalysis offers a unique activation mode of molecules, which serves as an alternative many thermal transition-metals catalyzed reactions. Most photoredox-catalyzed processes capitalize on heavy metals, namely, Ru(II) or Ir(III)-complexes, can serve single electron oxidants reductants in their photoexcited states. Copper-and iron-based photo¬catalysts are rapidly emerging, offering economic ecologic advantages but, addition, interact with substrates beyond transfer via inner sphere mechanisms, have been successfully utilized achieve challenging transformations. Emphasizing the principles catalysis, selected synthetic applications from our laboratory will be discussed, highlighting opportunities copper- iron-photocatalysts offer area.

Language: Английский

Citations

0