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

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Дек. 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)

Язык: Английский

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Magnesium/methanol-d1: a practical reductive deuteration system for the deuterium labeling of α,β-unsaturated esters, nitriles and amides

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The use of magnesium and methanol in the reduction various functional groups has been well established. In this study, we present a reductive deuteration system using Mg/CH

Язык: Английский

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Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Июнь 7, 2024

We report a photochemical method for the semipinacol rearrangement of unactivated allylic alcohols. Aliphatic as well aromatic groups participate migrating groups, yielding variety α,α-disubstituted ketones. The reaction proceeds under mild conditions and is compatible with ethers, esters, halides, nitriles, carbamates, substituted arenes. operationally simple fully catalytic prescribe 1 mol % benzothiazinoquinoxaline organophotocatalyst, 0.5 Co-salen, 10 lutidinium triflate and, importantly, display reactivity complementary to procedures employing Brønsted acid. showcase utility protocol in late-stage drug diversifications.

Язык: Английский

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Synthesis of Polysubstituted Enamides by Hydrogen Atom Transfer Alkene Isomerization Using Dual Cobalt/Photoredox Catalysis

Chemistry - A European Journal, Год журнала: 2023, Номер 29(37)

Опубликована: Апрель 19, 2023

M-HAT isomerization is a highly reliable method to access thermodynamically stable alkenes with high functional group tolerance. However, synthesis of heteroatom-substituted by reaction still underdeveloped. Herein, we report an enamide using via combination cobalt and photoredox catalysis. This tolerates variety groups including haloarenes, heteroarenes, free hydroxy groups, non-protected indoles, drug derivatives. Furthermore, this can isomerize styrene derivatives in good yield E/Z selectivity.

Язык: Английский

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Photocatalytic Semi‐Hydrogenation of Acetylene to Polymer‐Grade Ethylene with Molecular and Metal–Organic Framework Cobaloximes

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 22, 2024

Abstract The semi‐hydrogenation of acetylene in ethylene‐rich gas streams is a high‐priority industrial chemical reaction for producing polymer‐grade ethylene. Traditional thermocatalytic routes reduction to ethylene, despite progress, still require high temperatures and H 2 consumption, possess relatively low selectivity, use noble metal catalyst. Light‐powered strategies are starting emerge, given that they have the potential directly abundant sustainable solar irradiation, but ineffective. Here an efficient, >99.9% selective, visible‐light powered, catalytic conversion ethylene reported. catalyst homogeneous molecular cobaloxime operates tandem with photosensitizer at room temperature bypasses non‐environmentally friendly flammable feed. proceeds through cobalt‐hydride intermediate ≈100% under competitive (ethylene co‐feed) conditions after only 50 min, no evolution or over‐hydrogenation ethane. further incorporated as linker metal–organic framework; result heterogeneous can be recycled up six times remains catalytically active 48 h, before significant loss performance observed.

Язык: Английский

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Single‐Atom Nickel on Carbon Nitride Photocatalyst Achieves Semihydrogenation of Alkynes with Water Protons via Monovalent Nickel

Angewandte Chemie, Год журнала: 2023, Номер 135(9)

Опубликована: Янв. 10, 2023

Abstract Prospects in light‐driven water activation have prompted rapid progress hydrogenation reactions. We describe a Ni 2+ −N 4 site built on carbon nitride for catalyzed semihydrogenation of alkynes, with supplying protons, powered by visible‐light irradiation. Importantly, the photocatalytic approach developed here enabled access to diverse deuterated alkenes D 2 O excellent deuterium incorporation. Under irradiation, evolution four‐coordinate species into three‐coordinate + was spectroscopically identified. In combination theoretical calculations, photo‐evolved is posited as HO−Ni an uncoordinated, protonated pyridinic nitrogen, formed coupled reduction and dissociation. The paired Ni−N prompts hydrogen liberation from water, it renders desorption alkene preferred over further alkane, ensuring selectivity.

Язык: Английский

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Radical Crotylation of Aldehydes with 1,3-Butadiene by Photoredox Cobalt and Titanium Dual Catalysis

Organic Letters, Год журнала: 2023, Номер 25(42), С. 7694 - 7699

Опубликована: Окт. 16, 2023

Metal-hydride hydrogen atom transfer (MHAT) has been recognized as a powerful method for alkene functionalization; however, photochemical MAT-mediated chemoselective functionalization of dienes remains undeveloped. In this study, we report radical strategy (1e–) through MHAT using photoredox cobalt and titanium dual catalysis aldehyde crotylation with butadiene, achieving excellent regio- diastereoselectivity.

Язык: Английский

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Visible-Light-Driven Catalytic Dehalogenation of Trichloroacetic Acid and α-Halocarbonyl Compounds: Multiple Roles of Copper

ACS Catalysis, Год журнала: 2025, Номер 15(5), С. 3873 - 3881

Опубликована: Фев. 19, 2025

Herein, we report the reaction development and mechanistic studies of visible-light-driven Cu-catalyzed dechlorination trichloroacetic acid for highly selective formation monochloroacetic acid. Visible-light-driven transition metal catalysis via an inner-sphere pathway features dual roles species in photoexcitation substrate activation steps, a detailed understanding their is crucial further light-driven catalysis. This catalytic method, which environmentally desired ascorbic as hydrogen atom source water/ethanol solvent, can be applied to dehalogenation variety halocarboxylic acids amides. Spectroscopic, X-ray crystallographic, kinetic have revealed mechanism copper photoexcitation, thermal first C–Cl bond, excited-state second bond chlorine transfer.

Язык: Английский

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Nickel‐Catalyzed Hydrogenation of Enamides and Quinolines via Photoinduced Hydrogen Atom Transfer

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 18, 2025

Comprehensive Summary Radical hydrogenation facilitated by metal (Fe, Co, Mn, etc .) hydride‐mediated hydrogen atom transfer ( m HAT) has emerged as a powerful technique in organic synthesis. However, nickel‐hydride (NiH) catalyzed radical remained largely unexplored. Herein, we develop NiH catalytic system that achieves the of enamides high efficiency. This strategy stands out for its ability to hydrogenate challenging quinolines at room temperature, avoiding catalyst poisoning and deactivation their products. Furthermore, deuteration alkenes was achieved with rates (up > 99%), underscoring potential synthesis deuterium‐containing molecules.

Язык: Английский

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Distal Heteroaryl Ipso‐Migration of Unactivated Alkenes via Cobalt/Photoredox‐Catalyzed Hydrogen/Deuterium Atom Transfer

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Июнь 5, 2025

Abstract A structural isomerization of alkenyl alcohols via 1,4‐ or 1,5‐heteroaryl migration initiated by metal‐hydride hydrogen atom transfer (MHAT) under cobalt/photoredox dual catalysis is described. The remote method provided various heteroaryl‐containing ketones inaccessible through conventional MHAT 1,2‐migration pathways. was further applied to the synthesis deuterium‐labeled ketones.

Язык: Английский

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