Photoelectrochemical Si–H and Ge–H activation by iron catalysis DOI Creative Commons
Wen Wei, Simon L. Homölle, Tristan von Münchow

et al.

Cell Reports Physical Science, Journal Year: 2023, Volume and Issue: 4(9), P. 101550 - 101550

Published: Aug. 21, 2023

The development of efficient and sustainable methods for hydrosilane hydrogermane functionalization is importance due to their abundant use as functional modifiers high bond dissociation energy. Despite advances in photoredox catalysis, expensive photocatalysts hydrogen atom transfer mediators are usually required functionalization. In contrast, we herein report on a photoelectrochemical iron-catalyzed alkene silyl arylation that harnesses the power light electricity challenging Si–H Ge–H activation. Notably, reaction features iron complexes used earth-abundant chloride green inexpensive reagent. Detailed mechanistic studies elucidated silane activation mode under catalysis.

Language: Английский

Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization DOI
Xiao‐Li Lai, Hai‐Chao Xu

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

Citations

63
Photoelectrochemically driven iron-catalysed C(sp3)−H borylation of alkanes DOI

Yangmin Cao,

Cheng Huang, Qingquan Lu

et al.

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

Published: Jan. 31, 2024

Language: Английский

Citations

23
Molecular Photoelectrocatalysis for Radical Reactions DOI
Peng Xiong, Hai‐Chao Xu

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

Citations

3
Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids DOI
Jiaqing Lu, Yan Yao, Liubo Li

et al.

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

Citations

32
Selective C(sp3)–H arylation/alkylation of alkanes enabled by paired electrocatalysis DOI Creative Commons

Long Zou,

Siqi Xiang,

Rui Sun

et al.

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

Citations

31
Paired Electrolysis Enabled Trifluoromethylheteroaromatization of Alkenes and Alkyne with Trifluoromethyl Thianthrenium Triflate (TT-CF3+OTf–) as a Bifunctional Reagent DOI
Xiang Fang,

Dehui Wang,

Kun Xu

et al.

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

Citations

27
Asymmetric Paired Electrocatalysis: Enantioselective Olefin–Sulfonylimine Coupling DOI
Cheng Huang, Yongsheng Tao,

Xiyang Cao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(3), P. 1984 - 1991

Published: Dec. 19, 2023

Asymmetric electrocatalysis offers exciting new strategies for the synthesis of chiral molecules through novel reaction pathways. However, simultaneous activation reactants on both electrodes via asymmetric paired electrolysis, which is more energy efficient and economic than single half-electrode synthesis, remains a formidable challenge. Herein, an olefin–sulfonylimine coupling presented first time. In this protocol, Co-catalyzed hydrogen atom transfer anode Ni-catalyzed sulfonylimine reduction cathode were seamlessly cross-coupled. The catalytic system enables formation amine products bearing tetrasubstituted carbon stereocenter with high enantioselectivity (up to 96% ee).

Language: Английский

Citations

24
Photoredox streamlines electrocatalysis: photoelectrosynthesis of polycyclic pyrimidin-4-ones through carbocyclization of unactivated alkenes with malonates DOI

Minglin Tao,

Feng Qin,

Kaixing Gong

et al.

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

Citations

15
Unleashing the potentiality of metals: synergistic catalysis with light and electricity DOI
Zhengjia Shen, Jia‐Lin Tu, Binbin Huang

et al.

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

Citations

13
Photoelectrochemical Fe/Ni cocatalyzed C−C functionalization of alcohols DOI Creative Commons

Long Zou,

Rui Sun, Yongsheng Tao

et al.

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

Citations

13