Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(44), С. 20201 - 20206

Опубликована: Окт. 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.

Язык: Английский

---

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

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(34), С. 18753 - 18759

Опубликована: Авг. 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.

Язык: Английский

---

Contemporary photoelectrochemical strategies and reactions in organic synthesis

Chemical Communications, Год журнала: 2023, Номер 59(24), С. 3487 - 3506

Опубликована: Янв. 1, 2023

This review mainly summarizes some important works and recent advancements in the electrophotocatalytic strategy since its development (2019–2022) introduces catalytic mechanism of electro–photocatalysts detail.

Язык: Английский

---

Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(8)

Опубликована: Янв. 8, 2024

A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination this deacylative process with S

Язык: Английский

---

Molecular Photoelectrocatalysis for Radical Reactions

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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

Язык: Английский

---

Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 16, 2023

Organoboron compounds are of high significance in organic synthesis due to the unique versatility boryl substituents access further modifications. The demand for incorporation moieties into molecular structures has witnessed significant progress, particularly C(sp3)-H borylation hydrocarbons. Taking advantage special characteristics photo/electrochemistry, we herein describe development an oxidative reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. exhibits broad substrate scope (>57 examples), includes use simple alkanes, halides, silanes, ketones, esters nitriles as viable substrates. Notably, unconventional regioselectivity is achieved, with coupling site selectively located distal methyl group. Our method operationally easily scalable, offers a feasible approach one-step high-value organoboron building blocks from hydrocarbons, which would provide ample opportunities drug discovery.

Язык: Английский

---

Electrophotocatalytic tri- or difluoromethylative cyclization of alkenes

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(10), С. 2482 - 2490

Опубликована: Янв. 1, 2023

Photoelectrocatalysis is mild yet potent and this work unlocks the potential of unactivated alkenes for oxidant-free oxidative cyclization alkenes.

Язык: Английский

---

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

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Дек. 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.

Язык: Английский

---

Photocatalytic 1,2-Iminosulfonylation and Remote 1,6-Iminosulfonylation of Olefins

Organic Letters, Год журнала: 2023, Номер 25(10), С. 1742 - 1747

Опубликована: Март 8, 2023

A new class of iminosulfonylation reagents were developed and extensively used in the 1,2-iminosulfonylation various olefins. Olefins containing bioactive molecules, such as indomethacin, gemfibrozil, clofibrate, fenbufen, afforded desired products synthetically useful yields. Furthermore, first remote 1,6-iminosulfonylation alkenes was realized by using oxime ester bifunctionalization reagents. Overall, more than 40 structurally diverse β-imine sulfones obtained moderate to excellent

Язык: Английский

---

Photoredox catalysis harvesting multiple photon or electrochemical energies

Beilstein Journal of Organic Chemistry, Год журнала: 2023, Номер 19, С. 1055 - 1145

Опубликована: Июль 28, 2023

Photoredox catalysis (PRC) is a cutting-edge frontier for single electron-transfer (SET) reactions, enabling the generation of reactive intermediates both oxidative and reductive processes via photon activation catalyst. Although this represents significant step towards chemoselective and, more generally, sustainable chemistry, its efficacy limited by energy visible light photons. Nowadays, excellent alternative conditions are available to overcome these limitations, harvesting two different but correlated concepts: use multi-photon such as consecutive photoinduced electron transfer (conPET) combination photo- electrochemistry in synthetic photoelectrochemistry (PEC). Herein, we review most recent contributions fields activations organic functional groups. New opportunities chemists captured, selective reactions employing super-oxidants super-reductants engage unactivated chemical feedstocks, scalability up gram scales continuous flow. This provides comparisons between techniques (multi-photon photoredox PEC) help reader fully understand their similarities, differences potential applications therefore choose which method appropriate given reaction, scale purpose project.

Язык: Английский

---