Single Electron Transfer-Induced Redox Processes Involving N-(Acyloxy)phthalimides

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(3), P. 1640 - 1683

Published: Jan. 20, 2021

The past decade has witnessed the emergence of N-(acyloxy)phthalimides (NHPI esters) and its derivatives at forefront synthetic methods facilitating construction diverse molecular frameworks from readily available carboxylic acid feedstock. NHPI esters are predisposed to undergo reductive fragmentation via a single electron transfer (SET) process under thermal, photochemical, or electrochemical conditions generate corresponding carbon- nitrogen-centered radicals that participate in multitude transformations forge carbon–carbon carbon–heteroatom bonds. chemistry involving received broad applicability not only well-designed cascade annulations but also medicinal natural product synthesis. This comprehensive Review, broadly categorized according nature bond formation, details progress made this field since initial discovery by providing representative examples with mechanistic details, an emphasis on challenges future directions.

Language: Английский

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Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6307 - 6416

Published: Jan. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Language: Английский

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Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity

Nature, Journal Year: 2021, Volume and Issue: 596(7871), P. 250 - 256

Published: June 28, 2021

Language: Английский

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Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(6), P. 4162 - 4184

Published: Jan. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Language: Английский

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Photoinduced Copper-Catalyzed Asymmetric C–O Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13382 - 13392

Published: Aug. 10, 2021

The construction of carbon–heteroatom bonds is one the most active areas research in organic chemistry because function molecules often derived from presence heteroatoms. Although considerable advances have recently been achieved radical-involved catalytic asymmetric C–N bond formation, there has little progress corresponding C–O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling readily available oxime esters and 1,3-dienes to generate diversely substituted allylic with high regio- enantioselectivity (>75 examples; up 95% ee). reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) features use single, earth-abundant copper-based chiral catalyst as both photoredox for radical generation source induction coupling. Combined experimental density functional theory (DFT) computational studies suggest formation π-allylcopper complexes redox-active bifunctional reagents through radical–polar crossover process.

Language: Английский

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Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes

Science China Chemistry, Journal Year: 2020, Volume and Issue: 63(11), P. 1586 - 1600

Published: Sept. 28, 2020

Language: Английский

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Copper-catalysed amination of alkyl iodides enabled by halogen-atom transfer

Nature Catalysis, Journal Year: 2021, Volume and Issue: 4(7), P. 623 - 630

Published: July 12, 2021

Language: Английский

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Copper-Catalyzed Carbonylative Coupling of Alkyl Halides

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(9), P. 2261 - 2274

Published: April 21, 2021

ConspectusTransition metal-catalyzed carbonylation reactions represent a direct and atom-economical approach to introduce oxygen functionality into organic compounds, with CO acting as an inexpensive readily available C1 feedstock. Despite the long history of catalysis, including many processes that have been industrialized at bulk scale, there remain several challenges tackle. For example, noble metals such Pd, Rh, Ir are typically used catalysts for reactions, rather than earth-abundant alternatives. Additionally, while C(sp2)-hybridized substrates (e.g., aryl halides) is well-known, unactivated alkyl electrophiles, especially where β-hydride elimination can compete desired migratory insertion catalyst site, remains challenging systems. Recently, base metal catalysis based on Mn, Co, other has enabled advances in carbonylative coupling though nucleophiles often limited alcohols or amines generate esters amides products. Thus, we targeted C–C C–E (E = N, H, Si, B) method approaching diverse carbonyl compounds synthetic importance.Initially, designed heterobimetallic platform halides arylboronic (i.e., Suzuki–Miyaura coupling) ketones. Subsequently, developed multicomponent using NHC-Cu (NHC N-heterocyclic carbene). These operate by radical mechanisms, converting either acyl halide intermediates undergo subsequent Cu site. This mechanistic paradigm relatively novel area, allowing us discover previously unexplored chemical space catalysis. We successfully following reactions: (a) hydrocarbonylative alkynes halides; (b) borocarbonylative (c) reductive aminocarbonylation nitroarenes; (d) (e) silylation (f) borylation halides. provide broad range valuable products ketones, allylic alcohols, β-borylenones, amides, acylsilanes, acylborons efficient manner. Notably, preparation some these required multistep syntheses, harsh conditions, specialized reagents. By contrast, requires only building blocks rapidly increases molecular complexity single manipulation.

Language: Английский

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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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Desulfonylative Transformations of Sulfones by Transition-Metal Catalysis, Photocatalysis, and Organocatalysis

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(5), P. 3013 - 3032

Published: Feb. 18, 2022

Sulfones are common, readily available reagents that have recently attracted attention as versatile for cross-coupling reactions. This Review summarizes advances in desulfonylative transformations of sulfones affected by molecular catalysis, including transition-metal catalysts, photocatalysts, and organocatalysts. In addition to catalyst choice, the design sulfonyl group is a critical factor control reactivity. The concepts presented herein will provide new strategies construct diverse molecules with high efficiency modularity.

Language: Английский

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