Electrochemical NiH‐Catalyzed C(sp³)−C(sp³) Coupling of Alkyl Halides and Alkyl Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 14, 2023

Herein, an electrochemically driven NiH-catalyzed reductive coupling of alkyl halides and alkenes for the construction Csp3 -Csp3 bonds is firstly reported. Notably, serve dual function as substrates hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature this reaction realized by introducing intramolecular coordinating group substrate, where product can be easily adjusted give desired branched products. method proceeds mild conditions, exhibits a broad substrate scope, affords moderate excellent yields with over 70 examples, including late-stage modification natural products drug derivatives. Mechanistic insights offer evidence process. sp3 -carbon-halogen activated through single electron transfer (SET) nickel catalyst in its low valence state, generated cathodic reduction, generation from pivotal transformation.

Language: Английский

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Electroreductively Induced Radicals for Organic Synthesis

Molecules, Journal Year: 2023, Volume and Issue: 28(2), P. 857 - 857

Published: Jan. 15, 2023

Organic electrochemistry has attracted tremendous interest within the novel sustainable methodologies that have not only reduced undesired byproducts, but also utilized cleaner and renewable energy sources. Particularly, oxidative gained major attention. On contrary, reductive electrolysis remains an underexplored research direction. In this context, we discuss advances in transition-metal-free cathodically generated radicals for selective organic transformations since 2016. We highlight electroreductive reaction of alkyl radicals, aryl acyl silyl fluorosulfonyl trifluoromethoxyl radicals.

Language: Английский

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Electrochemical C−H deuteration of pyridine derivatives with D2O

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 7, 2024

Herein, we develop a straightforward, metal-free, and acid-/base-free electrochemical C4-selective C - H deuteration of pyridine derivatives with economic convenient D

Language: Английский

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Microenvironment regulation breaks the Faradaic efficiency-current density trade-off for electrocatalytic deuteration using D2O

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 19, 2024

Abstract The high Faradaic efficiency (FE) of the electrocatalytic deuteration organics with D 2 O at a large current density is significant for deuterated electrosynthesis. However, FE and are two ends seesaw because severe evolution side reaction nearly industrial densities. Herein, we report combined scenario nanotip-enhanced electric field surfactant-modified interface microenvironment to enable arylacetonitrile in an 80% −100 mA cm −2 . increased concentration low activation energy due along tips accelerated transfer suppressed by surfactant-created deuterophobic contribute breaking trade-off between density. Furthermore, application our strategy other reactions improved efficiencies rationalizes design concept.

Language: Английский

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Metallaphotoredox deuteroalkylation utilizing thianthrenium salts

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 13, 2024

Abstract Deuterium labeling compounds play a crucial role in organic and pharmaceutical chemistry. The synthesis of such typically involves deuterated building blocks, allowing for the incorporation deuterium atoms functional groups into target molecule single step. Unfortunately, limited availability synthetic approaches to synthons has impeded progress this field. Here, we present an approach utilizing alkyl-substituted thianthrenium salts that efficiently selectively introduce at α position alkyl chains through pH-dependent HIE process, using D 2 O as source. resulting α-deuterated salts, which bear two atoms, exhibit excellent selectivity electrophilic substitution reactions. Through situ formation isotopically labelled halides, these demonstrate compatibility series metallaphotoredox cross-electrophile coupling with (hetero)aryl, alkenyl, bromides, other salts. Our technique allows wide range substrates, high incorporation, precise control over site insertion within benzyl position, allylic or any chain between, well neighboring heteroatoms. This makes it invaluable synthesizing various deuterium-labeled compounds, especially those significance.

Language: Английский

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