Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(34), P. 18753 - 18759

Published: Aug. 15, 2023

The asymmetric difunctionalization of alkenes, a method transforming readily accessible alkenes into enantioenriched chiral structures high value, has long been focal point organic synthesis. Despite tremendous efforts in this domain, it remains considerable challenge to devise enantioselective oxidative dicarbofunctionalization even though these transformations can utilize stable and unfunctionalized functional group donors. In context, we report herein photoelectrocatalytic for the heteroarylcyanation aryl which employs heteroarenes through C-H functionalization. photoelectrochemical catalysis (PEAC) combines photoredox electrocatalysis facilitate formation two C-C bonds operating via hydrogen (H2) evolution obviating need external chemical oxidants.

Language: Английский

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Photoelectrochemically driven iron-catalysed C(sp3)−H borylation of alkanes

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(4), P. 537 - 544

Published: Jan. 31, 2024

Language: Английский

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Molecular Photoelectrocatalysis for Radical Reactions

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes capacity to offer novel reactivity selectivity, represents an emerging field in chemistry that addresses growing demands for environmental sustainability synthetic efficiency. This synergistic approach permits access a wider range redox potentials, facilitates transformations under gentler electrode decreases use external harsh reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we others reported first examples modern molecular photoelectrocatalysis. These studies showcased immense hybrid strategy, only inherits strengths its parent fields but also unlocks unprecedented enabling challenging mild conditions while minimizing reliance on stoichiometric oxidants or reductants.In Account, present our efforts develop photoelectrocatalytic strategies leverage homogeneous catalysts facilitate diverse radical reactions. By integrating electrocatalysis with key photoinduced processes such as single electron transfer (SET), ligand-to-metal charge (LMCT), hydrogen atom (HAT), have established methods transform substrates organotrifluoroborates, arenes, carboxylic acids, alkanes into reactive intermediates. intermediates subsequently engage heteroarene C-H functionalization Importantly, photoelectrochemical catalysts, generated bulk solution readily participate efficient reactions without undergoing further overoxidation carbocations, common challenge conventional electrochemical systems.By integration photoelectrocatalysis asymmetric catalysis, developed catalysis (PEAC), proves be enantioselective synthesis chiral nitriles. involves two relay catalytic cycles: initial process engenders benzylic radicals from precursors alkyl aryl alkenes, C-radicals are then subjected cyanation subsequent copper-electrocatalytic cycle.Within realm oxidative transformations, anode serves crucial component recycling generating photocatalyst, cathode promotes proton reduction. dual functionality enables via H

Language: Английский

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Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26774 - 26782

Published: Nov. 29, 2023

Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis alkenes all substitution patterns has been accomplished by means Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl as limiting reagents and exhibit a broad scope respect to both coupling partners. Notably, simple primary could be readily engaged carbon-centered radical precursors in reaction. This new protocol successfully demonstrated direct modification naturally occurring complex is amenable enantioselective arylacetic acid. Mechanistic studies, including series controlled experiments cyclic voltammetry data, allow us probe key intermediates pathway

Language: Английский

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Selective C(sp3)–H arylation/alkylation of alkanes enabled by paired electrocatalysis

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Dec. 2, 2023

We report a combination of electrocatalysis and photoredox catalysis to perform selective C(sp3)-H arylation/alkylation alkanes, in which binary catalytic system based on earth-abundant iron nickel is applied. Reaction selectivity between two-component arylation three-component alkylation tuned by modulating the applied current light source. Importantly, an ultra-low anodic potential (~0.23 V vs. Ag/AgCl) this protocol, thus enabling compatibility with variety functional groups (>70 examples). The robustness method further demonstrated preparative scale late-stage diversification natural products pharmaceutical derivatives.

Language: Английский

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Paired Electrolysis Enabled Trifluoromethylheteroaromatization of Alkenes and Alkyne with Trifluoromethyl Thianthrenium Triflate (TT-CF₃⁺OTf^–) as a Bifunctional Reagent

Organic Letters, Journal Year: 2023, Volume and Issue: 26(1), P. 411 - 415

Published: Dec. 26, 2023

We report a strategic exploitation of trifluoromethyl thianthrenium triflate (TT-CF3+OTf–) as both electromediator and CF3 radical precursors for paired electrolysis. Enabled by this strategy, the three-component trifluoromethylheteroaromatization alkenes alkynes was realized. The superiority TT-CF3+OTf– to other electrophilic reagents is attributed cathodic generation thianthrene (TT) mediator, which shifts heterogeneous oxidation interest homogeneous one.

Language: Английский

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Photoredox streamlines electrocatalysis: photoelectrosynthesis of polycyclic pyrimidin-4-ones through carbocyclization of unactivated alkenes with malonates

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(7), P. 4199 - 4208

Published: Jan. 1, 2024

A new photoelectrocatalytic mode permits the synthesis of polycyclic pyrimidin-4-ones through dehydrogenative cyclization malonates with unactivated alkenes.

Language: Английский

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Unleashing the potentiality of metals: synergistic catalysis with light and electricity

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4024 - 4040

Published: Jan. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Language: Английский

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Photoelectrochemical Fe/Ni cocatalyzed C−C functionalization of alcohols

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 19, 2024

Abstract The simultaneous activation of reactants on the anode and cathode via paired electrocatalysis has not been extensively demonstrated. This report presents a oxidative reductive catalysis based earth-abundant iron/nickel cocatalyzed C–C functionalization ubiquitous alcohols. A variety alcohols (i.e., primary, secondary, tertiary, or unstrained cyclic alcohols) can be activated at very low oxidation potential (~0.30 V vs. Ag/AgCl) photoelectrocatalysis coupled with versatile electrophiles. reactivity yields wide range structurally diverse molecules broad functional group compatibility (more than 50 examples).

Language: Английский

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Photoelectrochemical nickel-catalyzed carboacylation/silanoylation of alkenes with unactivated C/Si–H bonds

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(14), P. 8315 - 8322

Published: Jan. 1, 2024

A photoelectrochemical approach for the carboacylation/silanoylation of alkenes with alkanes/hydrosilanes is described. The method offers a new perspective chemists to rapidly obtain various ketones high levels structural complexity.

Language: Английский

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