Nickel-Catalyzed Enantioselective Electrochemical Reductive Cross-Coupling of Aryl Aziridines with Alkenyl Bromides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6270 - 6279

Published: March 7, 2023

An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling of aryl aziridines with alkenyl bromides has been developed, affording enantioenriched β-aryl homoallylic amines excellent E-selectivity. This electroreductive strategy proceeds in the absence heterogeneous metal reductants and sacrificial anodes by employing constant current electrolysis an undivided cell triethylamine as a terminal reductant. The reaction features mild conditions, remarkable stereocontrol, broad substrate scope, functional group compatibility, which was illustrated late-stage functionalization bioactive molecules. Mechanistic studies indicate that this transformation conforms stereoconvergent mechanism aziridine is activated through nucleophilic halide ring-opening process.

Language: Английский

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Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Language: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

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Allylgermane synthesis via facile and general nickela-electrocatalyzed electrophile coupling

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101257 - 101257

Published: Feb. 1, 2025

Language: Английский

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Zinc-free, Scalable Reductive Cross-Electrophile Coupling Driven by Electrochemistry in an Undivided Cell

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(20), P. 12617 - 12626

Published: Oct. 3, 2022

Nickel-catalyzed reductive cross-electrophile coupling reactions are becoming increasingly important in organic synthesis, but application at scale is limited by three interconnected challenges: a reliance on amide solvents (complicated workup, regulated), the generation of stoichiometric Zn salts isolation, waste disposal issue), and mixing/activation challenges zinc powder. We show here an electrochemical approach that addresses these issues: reaction works acetonitrile with diisopropylethylamine as terminal reductant simple undivided cell (graphite(+)/nickel foam(-)). The utilizes combination two ligands, 4,4'-di-

Language: Английский

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Electrophotochemical Decarboxylative Azidation of Aliphatic Carboxylic Acids

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10661 - 10667

Published: Aug. 16, 2022

We report an electrophotochemical metal-catalyzed strategy that harnesses the power of light and electricity for radical decarboxylative functionalization aliphatic carboxylic acids. This environmentally friendly protocol smoothly converts a diverse array acids into corresponding alkyl azides without using chemical oxidants or azido-group transfer reagents. The visible energy electric can be applied in spatially separated fashion with modular electro-flow-cell large-scale synthesis.

Language: Английский

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Electrochemical chemo- and regioselective arylalkylation, dialkylation and hydro(deutero)alkylation of 1,3-enynes

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(11), P. 1068 - 1081

Published: June 22, 2023

Language: Английский

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Carbon–Germanium Bond Formation via Low-Valent Cobalt-Catalyzed Cross-Electrophile Coupling

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6773 - 6780

Published: May 3, 2023

An efficient, electrochemically induced cobalt-catalyzed carbon–germanium bond formation provides access to a variety of functionalized germane-containing compounds, including aryl, vinyl, and alkyl germanes. The germylation is conducted under mild reaction conditions exhibits broad scope functional group tolerance. Mechanistic experimental studies provide insight into the unexpected pathway sequential activation different electrophiles.

Language: Английский

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Group 14 Elements Hetero‐Difunctionalizations via Nickel‐Catalyzed Electroreductive Cross‐Coupling

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(33)

Published: June 13, 2023

Abstract The difunctionalization of unsaturated bonds plays a vital role in the enrichment molecular complexity. While various catalytic methods for alkene and alkyne have been developed recent years, hetero‐functionalization introduction two different atoms has less explored. This is mainly due to challenges associated with achieving high chemo‐, regio‐, stereoselectivity, especially when adding similar from same group across bonds. In this study, we describe nickel‐catalyzed, three‐component reductive protocol 14 element hetero‐difunctionalization 1,3‐enynes using electrochemistry. new method mild, selective, general, allowing silyl‐, germanyl‐, stannyl‐alkylation enynes. Various chlorosilanes as well chlorogermans, chlorostannanes can be successfully used combination aryl/alkyl‐substituted primary, secondary, tertiary alkyl bromides electroreductive coupling.

Language: Английский

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Metal Cations from Sacrificial Anodes Act as a Lewis Acid Co-Catalyst in Electrochemical Cross-Coupling of Aryl Bromides and Aziridines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8813 - 8820

Published: June 20, 2023

An efficient method for the reductive cross-electrophile coupling of aziridines with aryl halides using nickel electrocatalysis is reported. This reaction provides valuable phenethylamines at room temperature in good yields. The was successfully applied to electro-reductive cross-coupling less reactive, unsubstituted N-tosylaziridine. Additionally, we were even able couple challenging alkyl bromides aziridines. Control experiments and voltammetric studies confirm that mechanism distinct from conventional photochemical couplings. Furthermore, role both Ni(II) organometallic complexes electrodes examined, providing insight into beneficial sacrificial anode electrochemical cross-couplings.

Language: Английский

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