Recent advances in dual photoredox/nickel catalyzed alkene carbofunctionalised reactions

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(68), P. 8946 - 8977

Published: Jan. 1, 2024

Alkene carbofunctionalization reactions have great potential for synthesizing complex molecules and constructing structures in natural products medicinal chemistry. Recently, dual photoredox/nickel catalysis has emerged as a novel strategy alkene carbofunctionalization. Nickel offers numerous advantages over other transition metals, such cost-effectiveness, abundance, low toxicity, moreover, it many oxidation states. catalysts exhibit excellent catalytic activity photoredox/transition metal catalysis, facilitating the formation of carbon-carbon or carbon-heteroatom bonds organic transformations. This review highlights latest advancements photoredox/nickel-catalyzed carbofunctionalizations includes literature published from 2020 to 2024.

Language: Английский

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Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines

Chemical Science, Journal Year: 2025, Volume and Issue: 16(10), P. 4442 - 4449

Published: Jan. 1, 2025

Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical readily available starting materials are among most ideal catalytic protocols. However, associated challenge precisely control both regioselectivity site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile 1,2- 1,3-arylalkylations of N-acyl allylic amines have been developed. This reductive three-component protocol enables 1,2-arylalkylation 1,3-arylalkylation with aryl halides alkyl excellent chemo-, regio- site-selectivity, representing first example controlled migratory difunctionalization alkenes under conditions. A wide range terminal internal unactivated amines, precursors were tolerated, providing straightforward efficient access diverse C(sp3)-rich branched aliphatic materials.

Language: Английский

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Nickel/Photoredox Dual-Catalyzed, Regioselective 1,2-Carboacylation of Alkenes via Synergistic Alkyl and Benzoyl Radical Coupling

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 2, 2025

A regioselective 1,2-carboacylation protocol of alkenes via nickel/photoredox dual catalysis has been successfully developed under mild conditions. wide range alkyl bromides, α-oxocarboxylic acids, and styrenes proved to be compatible the optimized conditions, affording corresponding products in up 91% yields. Mechanistically, key success this approach is temporal orchestration radical generation: nickel-catalyzed halogen atom transfer (XAT) for bromides photoredox-driven decarboxylation acids.

Language: Английский

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Electrochemical synthesis of allenyl silanes and allenyl boronic esters

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: May 17, 2025

Allenyl silanes and boronates are pivotal building blocks in organic synthesis. Nevertheless, their synthesis requires the manipulation of transition metal or highly reactive species. Hence, development more sustainable protocol is sought after. Here we show electrochemical allenyl boronic esters. This catalyst-free method proceeds under mild reaction conditions. The for shows an excellent efficiency a good functional group tolerance. isolated yields (28 examples, 45-95% yields) without use catalyst A similar developed boronates, which obtained low to moderate (13 5-55% yields). Finally, mechanism based on oxidative generation silyl boryl radicals suggested access these classes allenes.

Language: Английский

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1,2-Acylcyanation of Styrenes by Photoinduced Nickel Catalysis to Generate Acyl Radicals from Acyl Fluorides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

We report herein a photoinduced nickel-catalyzed 1,2-acylcyanation of styrenes with acyl fluorides and trimethylsilyl cyanide (TMSCN). Nickel(II) complexes, formed from nickel(0) complexes fluorides, are photoexcited to generate radicals via ligand-to-metal charge transfer (LMCT) process. This transformation proceeds under mild conditions thus can be applied the late-stage functionalization (LSF) natural product derivatives. Synthetic derivatizations show utility products. The preparation aza-DIPYs is also demonstrated.

Language: Английский

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Silyl Radical‐Participated Silylfunctionalization of Alkenes and Alkynes

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

Abstract Alkenes and alkynes are inexpensive readily available basic chemicals. Silyl radical‐participated silylation of alkenes provides a powerful tool for the direct construction organosilicon compounds. Compared to hydrosilylation reactions, silylfunctionalization reactions more attractive advantageous in building diverse compounds, which has led their becoming research focus organic synthesis. Herein, we provide comprehensive overview recent advances silyl alkynes.

Language: Английский

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