Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(11), С. 2830 - 2848

Опубликована: Янв. 1, 2023

Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds and their mechanistic insights synthetic applications have been summarized.

Язык: Английский

---

Unraveling the Structure and Reactivity Patterns of the Indole Radical Cation in Regioselective Electrochemical Oxidative Annulations

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(5), С. 3175 - 3186

Опубликована: Янв. 27, 2023

Oxidation-induced strategy for inert chemical bond activation through highly active radical cation intermediate has exhibited unique reactivity. Understanding the structure and reactivity patterns of intermediates is crucial in mechanistic study will be beneficial developing new reactions. In this work, properties indole cations have been revealed using time-resolved transient absorption spectroscopy, situ electrochemical UV–vis, electron paramagnetic resonance (EPR) technique. Density functional theory (DFT) calculations were used to explain predict regioselectivity several oxidative annulations. Based on understanding inherent cations, two different regioselective annulations indoles successfully developed under oxidation conditions. Varieties furo[2,3-b]indolines furo[3,2-b]indolines synthesized good yields with high regioselectivities. Our insights into promote further development oxidation-induced functionalizations.

Язык: Английский

---

Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO₂

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Апрель 3, 2023

Carboxylation of easily available alkenes with CO2 is highly important to afford value-added carboxylic acids. Although dicarboxylation activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging unactivated 1,n-dienes (n>3) remains unexplored. Herein, we report first skipped dienes via electrochemistry, affording valuable dicarboxylic Control experiments and DFT calculations support single electron transfer (SET) reduction its radical anion, which followed by sluggish addition SET unstabilized alkyl radicals carbanions nucleophilic attack on give desired products. This reaction features mild conditions, broad substrate scope, facile derivations products promising application in polymer chemistry.

Язык: Английский

---

Electrophilic Halospirocyclization of N-Benzylacrylamides to Access 4-Halomethyl-2-azaspiro[4.5]decanes

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(19), С. 13610 - 13621

Опубликована: Сен. 11, 2023

An electrophilic spirocyclization of N-benzylacrylamides with N-halosuccinimides (NXS) as the halogenating reagents has been developed. This reaction is carried out at room temperature under simple conditions without relying on metal reagents, photochemistry, or electrochemistry, providing a fast and efficient route to synthesize wide variety 4-halomethyl-2-azaspiro[4.5]decanes satisfactory yields. The approach further highlighted through gram-scale synthesis diverse transformations spiro products.

Язык: Английский

---

Electrochemical electrophilic bromination/spirocyclization of N-benzyl-acrylamides to brominated 2-azaspiro[4.5]decanes

Green Chemistry, Год журнала: 2023, Номер 25(9), С. 3543 - 3548

Опубликована: Янв. 1, 2023

An electrochemical electrophilic bromination/spirocyclization of N -benzyl-acrylamides to brominated 2-azaspiro[4.5]decanes with 2-bromoethan-1-ol as the brominating reagent has been developed.

Язык: Английский

---

Organophotoelectrochemical silylation cyclization for the synthesis of silylated 3-CF₃-2-oxindoles

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(14), С. 3585 - 3590

Опубликована: Янв. 1, 2023

An organophotoelectrochemical approach for silylation cyclization of CF3-substituted N -arylacrylamides with organosilanes under transition-metal-free and oxidant-free conditions has been developed.

Язык: Английский

---

Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Язык: Английский

---

Enantioselective Cyanofunctionalization of Aromatic Alkenes via Radical Anions

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1410 - 1422

Опубликована: Янв. 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.

Язык: Английский

---

Organophotoelectrocatalytic C(sp²)–H alkylation of heteroarenes with unactivated C(sp³)–H compounds

Chemical Communications, Год журнала: 2024, Номер 60(42), С. 5502 - 5505

Опубликована: Янв. 1, 2024

An organophotoelectrocatalytic method for the C(sp 2 )–H alkylation of heteroarenes with unactivated 3 compounds via dehydrogenation cross-coupling was developed.

Язык: Английский

---

Frontiers in Photoelectrochemical Catalysis: A Focus on Valuable Product Synthesis

Advanced Materials, Год журнала: 2024, Номер 36(21)

Опубликована: Фев. 11, 2024

Abstract Photoelectrochemical (PEC) catalysis provides the most promising avenue for producing value‐added chemicals and consumables from renewable precursors. Over last decades, PEC catalysis, including reduction of feedstock, oxidation organics, activation functionalization C─C C─H bonds, are extensively investigated, opening new opportunities employing technology in upgrading readily available resources. However, several challenges still remain unsolved, hindering commercialization process. This review offers an overview targeted at synthesis high‐value sustainable First, fundamentals evaluating reactions context product both anode cathode recalled. Then, common photoelectrode fabrication methods that have been employed to produce thin‐film photoelectrodes highlighted. Next, advancements systematically reviewed discussed conversion various feedstocks highly valued chemicals. Finally, prospects field presented. aims facilitating further development precursors products other pharmaceuticals.

Язык: Английский

---