Scalable decarboxylative trifluoromethylation by ion-shielding heterogeneous photoelectrocatalysis

Science, Journal Year: 2024, Volume and Issue: 384(6696), P. 670 - 676

Published: May 9, 2024

Electrochemistry offers a sustainable synthesis route to value-added fine chemicals but is often constrained by competing electron transfer between the electrode and redox-sensitive functionalities distinct from target site. Here, we describe an ion-shielding heterogeneous photoelectrocatalysis strategy impose mass-transfer limitations that invert thermodynamically determined order of transfer. This showcased enable decarboxylative trifluoromethylation sensitive (hetero)arenes using trifluoroacetate, inexpensive yet relatively inert trifluoromethyl group (CF

Language: Английский

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Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4665 - 4680

Published: March 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Language: Английский

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Bismuth in Radical Chemistry and Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Nov. 22, 2023

Abstract Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19 th century, preparation and characterization both transient persistent bismuth‐radical species has only been established recent decades. These advancements led emergence field chemistry, mirroring progress seen for other main‐group elements. The seminal fundamental studies this area have ultimately paved way development catalytic methodologies involving intermediates, a promising approach that remains largely untapped broad landscape synthetic organic chemistry. In review, we delve into milestones eventually present state‐of‐the‐art Our focus aims at outlining intrinsic discoveries inorganic/organometallic chemistry contextualizing their practical applications synthesis catalysis.

Language: Английский

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Reductive Cyclopropanation through Bismuth Photocatalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22140 - 22144

Published: Aug. 5, 2024

We present here a catalytic method based on low-valent Bi complex capable of cyclopropanation double bonds under blue LED irradiation. The catalysis features various unusual Bi-based organometallic steps, namely, (1) two-electron inner sphere oxidative addition Bi(I) to CH2I2, (2) light-induced homolysis the Bi(III)–CH2I bond, (3) subsequent iodine abstraction-ring-closing, and (4) reduction Bi(III) with an external reducing agent close cycle. Stoichiometric experiments support proposed mechanism. This protocol represents unique example reductive photocatalytic process bismuth radical catalysis.

Language: Английский

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Iron(II) triflate as a photocatalyst for trifluoromethylation of functionalized arenes under blue LED light: Access to bioactive compounds

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 434, P. 115506 - 115506

Published: April 20, 2024

Language: Английский

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Stable Mn(II) metal–organic framework for efficient visible light initiated trifluoromethylation reaction

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 436, P. 115589 - 115589

Published: June 4, 2024

Language: Английский

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Electron-Donor-Mediated Divergent Transformation of Br–R_F via EDA Complex for the Synthesis of Fluorine-Containing Oxindoles and Amides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(46), P. 9990 - 9995

Published: Nov. 11, 2024

We have developed an unprecedented electron-donor-controlled divergent reaction between

Language: Английский

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Trendbericht Anorganische Chemie 2024: Hauptgruppen‐ und Molekülchemie

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(2), P. 46 - 55

Published: Jan. 31, 2025

Abstract Das erste heterobimetallische Dimetallocen; mit sterisch anspruchsvollen Liganden lassen sich einfach‐koordinierte Hauptgruppenverbindungen der Gruppen 13 bis 15 herstellen; neue Diazoverbindungen erlauben es, B‐R‐Einheiten und Kohlenstoffatome zu übertragen.

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Metal-free catalytic de novo construction of multi-functionalized trifluoromethylarenes through [3 + 3] benzannulation at low catalyst loadings

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A low catalyst loading and transition metal-free benzannulation of β,γ-alkynyl-α-keto esters CF 3 -alkenes has been developed through Michael-triggered [3 + 3] annulation.

Language: Английский

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Visible-Light-Induced Trifluoromethyl Radical Addition to Thiocarbonyl of Thioamide Derivatives

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

Published: Feb. 28, 2025

An effective trifluoromethyl radical addition to the thiocarbonyl of thioamide derivatives is described, which produces various trifluoromethylthiolated N-heterocycles such as 6-(trifluoromethylthio)phenanthridine, 2-(trifluoromethylthio)indole, and 2-(trifluoromethylthio)benzothiazole under visible-light irradiation. The process features advantages mild reaction conditions, a cheap easily available source (CF3Br), green energy, well broad substrate scope. mechanism investigated in detail, scale-up experiments are performed.

Language: Английский

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