Electrochemical Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

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Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20201 - 20206

Published: Oct. 31, 2022

The development of efficient and sustainable methods for decarboxylative transformations is great importance due to the ease availability nontoxicity carboxylic acids. Despite tremendous efforts in this area, it remains challenging develop enantioselective direct from Herein we disclose a photoelectrocatalytic method cyanation. photoelectrochemical reactions convert acids enantioenriched nitriles by employing cerium/copper relay catalysis with cerium salt catalytic decarboxylation chiral copper complex stereoselective C-CN formation.

Language: Английский

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Electrophotocatalytic Decoupled Radical Relay Enables Highly Efficient and Enantioselective Benzylic C–H Functionalization

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(47), P. 21674 - 21682

Published: Nov. 17, 2022

Asymmetric sp3 C–H functionalization has been demonstrated to substantially expedite target molecule synthesis, spanning from feedstocks upgradation late-stage modification of complex molecules. Herein, we report a highly efficient and sustainable method for enantioselective benzylic cyanation by merging electrophoto- copper catalysis. A novel catalytic system allows one independently regulate the hydrogen atom transfer step radical formation speciation Cu(II)/Cu(I) effectively capture transient intermediate, through tuning electronic property anthraquinone-type photocatalyst simply modulating applied current, respectively. Such decoupled relay catalysis enables unified approach diverse alkylarenes, many which are much less reactive or even unreactive using existing relying on coupled relay. Moreover, current protocol is also amenable bioactive molecules, including natural products drugs.

Language: Английский

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Enantioselective Radical Trifluoromethylation of Benzylic C–H Bonds via Cooperative Photoredox and Copper Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(30), P. 13468 - 13474

Published: July 21, 2022

The first enantioselective radical trifluoromethylation of benzylic C–H bonds has been established by a cooperative photoredox and copper catalysis system, providing straightforward access to structurally diverse products in good yields with excellent enantioselectivities under mild conditions. Our method features broad substrate scope functional group compatibility. Merging the is essential for reaction, where used generation radicals from alkyl arenes through hydrogen atom transfer process radicals.

Language: Английский

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Cu-Electrocatalytic Diazidation of Alkenes at ppm Catalyst Loading

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(27), P. 11980 - 11985

Published: June 30, 2022

The 1,2-diamine motif is prevalent in natural products, small-molecule pharmaceuticals, and catalysts for asymmetric synthesis. Transition metal catalyzed alkene diazidation has evolved to be an attractive strategy access vicinal primary diamines but remains challenging, especially practical applications, due the restriction a certain type of olefins, frequent use chemical oxidants, requirement high loadings (1 mol % or above). Herein we report scalable Cu-electrocatalytic reaction with 0.02 (200 ppm) copper(II) acetylacetonate as precatalyst without exogenous ligands. In addition its low catalyst loading, electrocatalytic method scalable, compatible broad range functional groups, applicable α,β-unsaturated carbonyl compounds mono-, di-, tri-, tetrasubstituted unactivated alkenes.

Language: Английский

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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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Enantioselective Cyanofunctionalization of Aromatic Alkenes via Radical Anions

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1410 - 1422

Published: Jan. 5, 2024

Alkene radical ions constitute an integral and unique class of reactive intermediates for the synthesis valuable compounds because they have both unpaired spins charge. However, relatively few synthetic applications alkene anions emerged due to a dearth generally applicable mild anion generation approaches. Precise control over chemo- stereoselectivity in anion-mediated processes represents another long-standing challenge their high reactivity. To overcome these issues, here, we develop new redox-neutral strategy that seamlessly merges photoredox copper catalysis enable controlled orthogonal enantioselective cyanofunctionalization via distonic-like species. This enables highly regio-, chemo-, hydrocyanation, deuterocyanation, cyanocarboxylation alkenes without stoichiometric reductants or oxidants under visible light irradiation. protocol provides blueprint exploration transformation potential anions.

Language: Английский

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Di-π-ethane Rearrangement of Cyano Groups via Energy-Transfer Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(27), P. 18210 - 18217

Published: May 24, 2024

Molecular rearrangement occupies a pivotal position among fundamental transformations in synthetic chemistry. Radical translocation has emerged as prevalent tool, efficiently facilitating the migration of diverse functional groups. In contrast, development di-π-methane remains limited, particularly terms cyano This is primarily attributed to energetically unfavorable three-membered-ring transition state. Herein, we introduce an unprecedented di-π-ethane enabled by energy-transfer catalysis under visible light conditions. innovative open-shell boasts broad tolerance toward range groups, encompassing even complex drug and natural product derivatives. Overall, reported represents complementary strategy radical catalysis.

Language: Английский

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Assembly of air-stable copper(I) alkynide nanoclusters assisted by tripodal polydentate phosphoramide ligands

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(4), P. 517 - 526

Published: Jan. 17, 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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