Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(21)

Published: April 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Language: Английский

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Iron-mediated modular decarboxylative cross-nucleophile coupling

Chem, Journal Year: 2023, Volume and Issue: 9(6), P. 1610 - 1621

Published: May 4, 2023

Language: Английский

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Direct Decarboxylation of Trifluoroacetates Enabled by Iron Photocatalysis**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 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.

Language: Английский

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Photochemical iron-catalyzed decarboxylative azidation via the merger of ligand-to-metal charge transfer and radical ligand transfer catalysis

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(6), P. 100603 - 100603

Published: April 12, 2023

Language: Английский

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Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

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Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(22), P. 9859 - 9873

Published: May 27, 2022

Many organometallic iridium(III) complexes have photoactive excited states with mixed metal-to-ligand and intraligand charge transfer (MLCT/ILCT) character, which form the basis for numerous applications in photophysics photochemistry. Cobalt(III) analogous MLCT excited-state properties seem to be unknown yet, despite fact that cobalt(III) can adopt identical low-spin d6 valence electron configurations due their close chemical relationship. Using a rigid tridentate chelate ligand (LCNC), central amido π-donor is flanked by two σ-donating N-heterocyclic carbene subunits, we obtained robust homoleptic complex [Co(LCNC)2](PF6), featuring state substantial character. Compared vast majority of isoelectronic iron(II) complexes, [Co(LCNC)2](PF6) long-lived because it does not deactivate as efficiently into lower-lying metal-centered states; furthermore, engages directly photoinduced reactions. The comparison [Fe(LCNC)2](PF6), well structural, electrochemical, UV–vis transient absorption studies, provides insight new design principles first-row transition-metal photophysical photochemical reminiscent those known from platinum group metals.

Language: Английский

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Chemical Modulation of Glucose Metabolism with a Fluorinated CaCO₃ Nanoregulator Can Potentiate Radiotherapy by Programming Antitumor Immunity

ACS Nano, Journal Year: 2022, Volume and Issue: 16(9), P. 13884 - 13899

Published: Sept. 8, 2022

Tumor hypoxia and acidity are well-known features in solid tumors that cause immunosuppression therapeutic resistance. Herein, we rationally synthesized a multifunctional fluorinated calcium carbonate (fCaCO3) nanoregulator by coating CaCO3 nanoparticles with dopamine-grafted perfluorosebacic acid (DA2-PFSEA) ferric ions utilizing their coordination interaction. After PEGylation, the obtained fCaCO3-PEG showed high loading efficacy to perfluoro-15-crown-5-ether (PFCE), type of perfluorocarbon oxygen solubility, thereby working as both nanoshuttles proton sponges reverse tumor acidity-induced resistance radiotherapy. The as-prepared PFCE@fCaCO3-PEG could not only function long-circulating attenuate but also neutralize acidic microenvironment restricting production lactic reacting extracellular protons. As result, treatment improve outcome radiotherapy toward two murine distinct immunogenicity. PFCE@fCaCO3-PEG-assisted collectively inhibit growth unirradiated reject rechallenged synergistically eliciting protective antitumor immunity. Therefore, our work presents preparation nanoregulators potentiate through chemically modulating hypoxic microenvironments tightly associated glucose metabolism.

Language: Английский

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Iron-catalyzed ring-opening of cyclic carboxylic acids enabled by photoinduced ligand-to-metal charge transfer

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(14), P. 5553 - 5558

Published: Jan. 1, 2022

A decarboxylative ring-opening reaction of cyclic tertiary carboxylic acids via an iron-catalyzed photoinduced ligand-to-metal charge transfer (LMCT) process is herein reported.

Language: Английский

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Photoinduced Ligand‐to‐Metal Charge Transfer of Carboxylates: Decarboxylative Functionalizations, Lactonizations, and Rearrangements

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(24), P. 4189 - 4230

Published: Dec. 3, 2022

Abstract In the quest for sustainable processes, selection of resources and catalysts is central importance. Carboxylic acids, which are abundant, stable ideally biobased feedstocks, can be considered as attractive platforms towards a range functionalized molecules. A recent resurgence photoinduced ligand‐to‐metal charge transfer (LMCT) carboxylates led to tremendous developments in field earth‐abundant metal mediated, visible‐light induced (non)‐decarboxylative transformations carboxylic acids. These reactions combine use available starting materials, low‐consuming energy source abundant catalysts. Besides these undeniable advantages, they also provide mild, highly selective innovative conditions complex molecule functionalization. The objective this review give an overview advances LMCT with special focus on mechanistic aspects transformations. magnified image

Language: Английский

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Photoredox-Catalyzed and Copper(II) Salt-Assisted Radical Addition/Hydroxylation Reaction of Alkenes, Sulfur Ylides, and Water

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3279 - 3285

Published: Feb. 25, 2022

A visible light-driven photoredox-catalyzed and copper(II)-assisted three-component radical addition/hydroxylation reaction of alkenes, sulfur ylides, water is reported. This process shows broad substrate scope high functional group tolerance, with respect to both readily available ylides providing high-yielding practical access valuable γ-hydroxy carbonyl compounds. Key the success controlled generation α-carbonyl carbon radicals from via sulfonium salts by a visible-light-driven proton-coupled electron transfer (PCET) strategy in mixture 2,2,2-trifluoroethanol/CH2Cl2. Addition Cu(TFA)2·H2O helps accelerate radical-cation crossover improve efficiency. Mechanistic studies suggest that hydroxy moiety products stems water. study also builds up platform for further investigation into synthetic chemistry ylides.

Language: Английский

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