Red-Light-Active N,C,N-Pincer Bismuthinidene: Excited State Dynamics and Mechanism of Oxidative Addition into Aryl Iodides

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Despite the progress made in field of synthetic organic photocatalysis over past decade, use higher wavelengths, especially those deep-red portion electromagnetic spectrum, remains comparatively rare. We have previously disclosed that a well-defined N,C,N-pincer bismuthinidene (1a) can undergo formal oxidative addition into wide range aryl electrophiles upon absorption low-energy red light. In this study, we map out photophysical dynamics 1a and glean insights nature excited state responsible for activation electrophiles. Transient emission techniques reveal that, irradiation with light, complex undergoes direct S0 → S1 metal-to-ligand charge transfer (MLCT) transition, followed by rapid intersystem crossing (ISC) to highly reducing emissive triplet (−2.61 V vs Fc+/0 MeCN). The low dissipative losses incurred during ISC (∼6% incident light energy) help rationalize ability convert useful chemical energy. Spectroelectrochemical computational data support charge-separated excited-state structure radical-anion character on ligand radical-cation bismuth. Kinetic studies competition experiments afford mechanism iodides; concerted inner-sphere processes from are ruled out, strongly supporting pathway proceeds via outer-sphere dissociative electron transfer.

Language: Английский

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Red-Light Mediated Formylation of Indoles Using Helical Carbenium Ion as Photoredox Catalyst

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A red-light ( λ = 640 nm)-mediated C-3 formylation of indoles utilizing a helical carbenium ion as photocatalyst and 2,2-dimethoxy- N , -dimethylethanamine formylating source is presented.

Language: Английский

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Photo-driven Aerobic C(sp3)-H Oxidation by Organic Photocatalysts: A Recent Review

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134496 - 134496

Published: Jan. 1, 2025

Language: Английский

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Harnessing Visible/UV Light for the Activation and/or Functionalization of C−H Bonds: Metal‐ and Photocatalyst‐Free Approach

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Abstract Photosynthesis in plants has inspired photochemical reactions organic chemistry. Synthetic chemists always seek cost‐effective, operationally simple, averting the use of toxic and difficult‐to‐remove metallic catalysts, atom economical, high product purity reactions. In last few decades, light as a catalyst increased exponentially literature exploded with examples, particularly by using expensive metal complexes, photosensitizers like dyes, hypervalent iodine, or inorganic semiconductors. this report, we have selected interesting examples performed without any photosensitizers. These inherent potential reactants to utilize energy initiate chemical Our main emphasis is highlight structural features that can absorb form an electron donor‐acceptor (EDA) complex during reaction reaction. Considering degree variability reactions, utmost care been taken present most accurate conditions. A short introductory section on will act anchor revolve around discussed explain underlying principle mechanism.

Language: Английский

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Near-Infrared-Light-Induced Iron(I) Dimer Enabled Abstraction of Ester Group from Cycloketone Oxime Esters

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Photoinduced dimeric metal complexes have been extensively utilized in halogen atom transfer (XAT) reactions. In this study, we successfully achieved the abstraction of ester group from cyclobutanone oxime esters via iron(I)-dimer catalysis under near-infrared (NIR) light (730 nm) excitation, enabling efficient synthesis cyanoalkylated alkenes, quinazolinones, and 3,3-disubstituted oxindoles. Mechanistic investigations confirmed NIR-induced functional process.

Language: Английский

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Taming Inert B–H Bond with Low Energy Light: A Near-Infrared Light-Induced Approach to Facile Carborane Cluster-Amino Acid Coupling

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

The selective functionalization of inert B–H bonds in carborane clusters has been a formidable challenge. Recent advances have witnessed such reactions through photoredox methods utilizing ultraviolet or visible light irradiation. However, high-energy sources often suffer from poor energy efficiency, limited substrate scope, undesired side reactions, and low scalability. Here, we present the first successful bond under low-energy near-infrared (NIR) using carborane-based electron donor–acceptor complex. Both photophysical investigations theoretical modeling reveal facile single-electron transfer cage to electron-deficient photocatalyst, generating radical NIR follow-up pathway enables direct coupling carboranes with amino acids oligopeptides, yielding diverse array carborane-functionalized oligopeptides. Beyond expanding known chemical space boron cluster derivatives, further demonstrate that imaging targeting capabilities could serve as promising multifunctional carriers for neutron capture therapy. Thus, via not only provides straightforward practical strategy synthetic chemistry but also lays foundation development next-generation boron-containing biomolecules advanced functional materials.

Language: Английский

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Donor–Acceptor-π-Acceptor–Donor-Type Photosensitive Covalent Organic Framework for Effective Photocatalytic Aerobic Oxidation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Developing effective photocatalysts for the oxidation reaction is of great significance in chemical synthesis but still challenging. Herein, linking photochromic triphenylamine with pyrene units by situ formed robust imidazole moieties, a covalent organic framework (COF), PyNTB-COF, containing rare donor-acceptor-π-acceptor-donor (D-A-π-A-D) fragment, was successfully synthesized photocatalytic aerobic oxidation. Structure characterizations confirm its crystalline framework, high porosity, and good stability. Property studies reveal photoelectric semiconductor feature photoresponsive charge separation migration activity derived from D-A-π-A-D fragments, proven experimental results theoretical calculations. Photocatalytic experiments not only display highly triggering generation ·O2- under visible light irradiation also exhibit efficiency oxidations toluene amidation aldehydes. This work demonstrates that integration into materials to construct π-conjugated D-A moieties could enhance efficiency, achieving promising

Language: Английский

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Electrochemical Benzylic C–H Carboxylation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Direct benzylic C-H carboxylation stands as a high atom economy, efficient, and convenient route for the synthesis of valuable carboxylic acids, which are great significance in many pharmaceuticals bioactive molecules. However, inherent inertness both bonds carbon dioxide presents challenge further transformations. Herein, we report our efforts to overcome this obstacle via halide-promoted linear paired electrolysis generate various acids. Remarkably, process is transition-metal- base-free, making it environmentally benign cost-effective. Besides, suitable constructing wide range primary, secondary, tertiary acids under mild reaction conditions, demonstrating broad substrate scopes good functional group tolerance. Furthermore, protocol enables direct some drug molecules, including Flurbiprofen, Ibuprofen, Naproxen, facilitates late-stage modification complex compounds, showcasing practical application synthetic chemistry underscores its potential advance related compounds.

Language: Английский

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Red Light and Supersilane: A Novel Pathway for Hydrofunctionalizations and Giese Reactions

ACS Organic & Inorganic Au, Journal Year: 2025, Volume and Issue: unknown

Published: May 10, 2025

Language: Английский

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AI Approaches to Homogeneous Catalysis with Transition Metal Complexes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 9089 - 9105

Published: May 14, 2025

Language: Английский

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