Organo-mediator enabled electrochemical transformations

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.

Language: Английский

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Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and power source, chemists are provided with system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds. Indeed, electroreduction offers alternative generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which untouchable traditional reduction methods. Meanwhile, reductive coupling extensively utilized both industrial academic settings due their ability swiftly, accurately, effectively construct C–C C–X bonds, present innovative approaches synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) requirement stoichiometric quantities agents, (b) scarce activation strategies inert substrates high potentials, (c) incomplete mechanistic elucidation, (d) challenges isolation intermediates. merging represents attractive approach address above limitations synthesis seen increasing use synthetic community over past few years.Since 2020, our group dedicated developing electroreductive cross-coupling using readily available small molecules, such arenes, CO2, D2O, value-added products. Electroreductive chemistry versatile powerful capacity precise selectivity control, allowed us develop three electrochemical modes lab: (1) An economically advantageous direct (EDR) strategy that emphasizes efficiency, achieves atom utilization, minimizes unnecessary atomic waste. (2) A class organo-mediated (EOMR) methods controlling reaction pathways. This allows modulation processes enhance efficiency selectivity. (3) metal-catalyzed (EMCR) method enables selective functionalization specific bonds functional groups under mild conditions, thereby occurrence side reactions. We commenced studies establishing organic-mediator-promoted carboxylation aryl alkyl halides. was then employed arylcarboxylation simple styrenes halides manner. electrolysis arenes epoxides CO2 carboxyl source achieved. Moreover, through adjustment we successfully accomplished deuteration olefins, unactivated enabling efficient formation D-labeled Finally, building on previous understanding developed series alkylation enable C(sp3)–C(sp3)

Language: Английский

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Atroposelective [4+1] Annulation for the Synthesis of Isotopic Isoindolinones Bearing both Central and Axial Chirality

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Isotopically chiral molecules have drawn much attention due to their practical applications in drug discovery. However, existing studies this area are mainly limited centrally and H/D exchange. Herein, we report a phosphoric acid-catalyzed atroposelective [4+1] annulation of ketoaldehydes 1H-indol-1-amines. By means strategy, series D- 18O-labeled atropisomers featuring both central axial chiralities synthesized with high enantioselectivities diastereoselectivities good excellent isotopic incorporation. Experimental density functional theory suggest that the reaction involves sequential condensation, cyclization isomerization cascade, which second step is enantio-determining process.

Language: Английский

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Precise synthesis of ortho-deuterated aromatic derivatives: an arylthianthrenium salt-based platform approach

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111132 - 111132

Published: March 1, 2025

Language: Английский

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Prolonging Lifetime of Hot Electrons Integrated with Microenvironment Regulation on Atomically-Dispersed Amphiphilic Quantum Dots for Photo-Reductive Hydroarylation of Alkenes in Aqueous Solution

Applied Catalysis B Environment and Energy, Journal Year: 2025, Volume and Issue: unknown, P. 125295 - 125295

Published: March 1, 2025

Language: Английский

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Electroreduction Reactions Mediated by Organic Molecules: Recent Advances and Applications

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(47)

Published: Aug. 27, 2024

Abstract Electroreduction is an important aspect of organic electrochemistry. Its chemistry does not require the addition additional reductants, making it effective alternative to various traditional reduction reactions. Among them, organo‐mediated electroreduction recognized as a promising approach. Organo‐mediators can be reduced directly at cathode form reactive radical anions that subsequently reduce substrate via electron transfer ( ET ) initiate reaction being investigated. typically have more positive potential, and their role in whole similar catalysts. Their transforms process from original heterogeneous into homogeneous one. Organo‐mediated effectively avoid over‐electrolysis product electrode intolerance sensitive substrates or functional groups during electrolysis, thereby preventing occurrence side It also prevent excessive consumption reagents electrical energy while promoting achieve higher completely different selectivity. Considering advantages this type reaction, review will provide detailed description reactions mediated by molecules recent years elucidate mechanism organo‐mediators transformations.

Language: Английский

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Dearomative Cyclization/Spirocyclization via Electrochemical Reductive Hydroarylation of Nonactivated Arenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(42), P. 8993 - 8998

Published: Oct. 14, 2024

An electrochemical cyclization/spirocyclization hydroarylation via reductive dearomatization of a series nonactivated arenes including

Language: Английский

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Anode material determined divergent 5‐<i>exo</i>‐<i>dig</i> cyclization of <i>N</i>‐cyano‐2‐halobenzamides toward 3‐iminoisoindolin‐1‐ones and 3‐aminoisoindolin‐1‐ones

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 6, 2024

Abstract Herein, an electroreductive aryl radical enabled 5‐ exo ‐ dig cyclization of N ‐cyano‐2‐halobenzamides is presented, providing a convenient route for the synthesis variety 3‐iminoisoindolin‐1‐ones in 30–75% yields. Simply by employing zinc plate instead graphite rod anode, products electrosynthesis are switched to diverse 3‐aminoisoindolin‐1‐ones through aryl‐radical‐mediated and subsequent reductive hydrogenation. Furthermore, this anode material determined divergent features mild electrochemical conditions, excellent substrate scopes, good functional group tolerance.

Language: Английский

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