Ligand‐to‐Metal Charge Transfer (LMCT) Photochemistry at 3d‐Metal Complexes: An Emerging Tool for Sustainable Organic Synthesis

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(19)

Published: Aug. 11, 2022

Abstract Despite the rich photochemistry of 3d‐metal complexes, utilization excited‐state reactivity these compounds in organic synthesis has been historically overlooked. The advent photoredox catalysis changed perception synthetic chemists towards photochemistry, and nowadays potential photoinduced, outer‐sphere single‐electron transfer events is widely recognized. More recently, an emerging new mode photoactivation taken spotlight, based on inner‐sphere triggered by population ligand‐to‐metal charge‐transfer (LMCT) excited states. Contrarily to photoredox, LMCT‐activation does not rely matching redox potentials, offers unique profiles particularly well suited Earth‐abundant metal complexes. Those appealing features are propelling development methods using this blueprint generate highly reactive open‐shell species under mild conditions. aim contribution provide a didactical tool for comprehension concept facilitate methodologies achieve sustainable chemical transformations.

Language: Английский

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Intercepting Hydrogen Evolution with Hydrogen-Atom Transfer: Electron-Initiated Hydrofunctionalization of Alkenes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(39), P. 17783 - 17791

Published: Sept. 22, 2022

Hydrogen-atom transfer mediated by earth-abundant transition-metal hydrides (M-Hs) has emerged as a powerful tool in organic synthesis. Current methods to generate M-Hs most frequently rely on oxidatively initiated hydride transfer. Herein, we report reductive approach Co-H, which allows for canonical hydrogen evolution reactions be intercepted hydrogen-atom an alkene. Electroanalytical and spectroscopic studies provided mechanistic insights into the formation reactivity of enabled development two new alkene hydrofunctionalization reactions.

Language: Английский

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Vitamin B₁₂‐Photocatalyzed Cyclopropanation of Electron‐Deficient Alkenes Using Dichloromethane as the Methylene Source**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Nov. 28, 2023

Abstract The cyclopropyl group is of great importance in medicinal chemistry, as it can be leveraged to influence a range pharmaceutical properties drug molecules. This report describes Vitamin B 12 ‐photocatalyzed approach for the cyclopropanation electron‐deficient alkenes using dichloromethane (CH 2 Cl ) methylene source. reaction proceeds good excellent yields under mild conditions, has functional compatibility, and highly chemoselective. scope could also extended preparation D ‐cyclopropyl methyl‐substituted adducts starting from CD 1,1‐dichloroethane, respectively.

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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The inorganic chemistry of the cobalt corrinoids – an update

Journal of Inorganic Biochemistry, Journal Year: 2023, Volume and Issue: 242, P. 112154 - 112154

Published: Feb. 3, 2023

Language: Английский

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Molecular Photothermal Conversion Catalyst Promotes Photocontrolled Atom Transfer Radical Polymerization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 8852 - 8857

Published: March 20, 2024

Photothermal conversion is a growing research area that promotes thermal transformations with visible light irradiation. However, few examples of dual photothermal and catalysis limit the power this phenomenon. Here, we take inspiration from nature's ability to use porphyrinic compounds for nonradiative relaxation convert into heat facilitate polymerization catalysis. We identify catalytic activity vitamin B

Language: Английский

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Diversified Synthesis of All-Carbon Quaternary gem-Difluorinated Cyclopropanes via Copper-Catalyzed Cross-Coupling

Organic Letters, Journal Year: 2023, Volume and Issue: 25(15), P. 2674 - 2679

Published: April 11, 2023

The construction of all-carbon quaternary centers in small-ring systems is important but challenging organic synthesis. Herein, by taking gem-difluorocyclopropyl bromides (DFCBs) as a type general and versatile building block, we developed practical method for gem-difluorinated cyclopropanes (DFCs). reaction relies on the involvement radical intermediate, which can couple with wide range nucleophiles under copper catalysis.

Language: Английский

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Photoinduced Ligand-to-Metal Charge Transfer in Base-Metal Catalysis

Synthesis, Journal Year: 2023, Volume and Issue: 56(13), P. 1967 - 1978

Published: Nov. 21, 2023

Abstract The absorption of light by photosensitizers has been shown to offer novel reactive pathways through electronic excited state intermediates, complementing ground-state mechanisms. Such strategies have applied in both photocatalysis and photoredox catalysis, driven generating intermediates from their long-lived states. One developing area is photoinduced ligand-to-metal charge transfer (LMCT) which coordination a ligand metal center subsequent excitation with results the formation radical reduced center. This mini review concerns foundations recent developments on transition-metal focusing organic transformations made possible this mechanism. 1 Introduction 2 Iron 3 Cobalt 4 Nickel 5 Copper 6 Future Outlook Conclusion

Language: Английский

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Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 14, 2023

Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those bromides or iodides. As a result, synthetic methods capable modifying the vast chemical space chloroalkane reagents, wastes, materials limited. We report cobalt-catalyzed reductive addition conjugated alkenes. Co-catalyzed activation is performed electroreductive conditions, resulting reactions constitute formal alkyl-alkyl bond formation. In developing an operationally simple methodology, detailed mechanistic studies provide insights into elementary steps proposed catalytic cycle. particular, we propose switch in mechanism C-Cl from nucleophilic substitution halogen atom abstraction, which critical for efficiently generating radicals. These were leveraged designing ligands that enable couplings primary, secondary, tertiary chlorides.

Language: Английский

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B(OH)₃‐Catalyzed Dual Friedel‐Crafts Type Reaction of Anilines and Aldehydes to Access Di‐ or Triarylmethanes (TRAMs)

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(7)

Published: Jan. 18, 2024

Abstract The catalytic influences of boric acid have been introduced on dual Friedel‐Crafts reaction between arylamines and aldehydes to install the Csp 3 ‐center that leads formation di ‐ or tri ‐substituted methanes. described conditions directed transformation favor para substitution pattern deliver major products rather than corresponding ortho functionalization process. devised was examined by DFT calculation, which shows favorable activation energy transition states (TS) for generation highly substituted molecular scaffolds. method applicable over diversely afford final in excellent yields (60‐92 %) selectivity. proposed mechanism is supported suitable control experiments, GC‐MS studies, calculations.

Language: Английский

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