Radical Decyanations of Unactivated Carbon‐CN Bonds: Recent Achievements and Mechanistic Studies

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(13), P. 2058 - 2091

Published: May 17, 2023

Abstract Decyanation is an important process in the synthesis of aromatic molecules studies pharmaceutical research, medical and materials sciences. In late‐stage modifications privileged carbo/heterocyclic scaffolds, radical‐type decyanation techniques have been devised to date. As a result, chemistry cyano‐involved conversions, hotly debated subject over past few decades, has advanced significantly. The cyano group (CN), on other hand, rarely acknowledged as good reaction site due its thermodynamic robustness. most recent advancements catalytic radical protocols that CN behaved leaving made are surveyed this article. Following introduction number different modes, reactions used activate C−CN bonds primarily categorized, text herein divided into three groups: (1) photo‐catalyzed transformations, (2) electro‐catalyzed (3) transition‐metal‐catalyzed or metal‐free transformations. With emphasis systems synthetic applications bond activation, review will provide readers with overview reactions.

Language: Английский

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Synergistic use of photocatalysis and convergent paired electrolysis for nickel-catalyzed arylation of cyclic alcohols

Science Bulletin, Journal Year: 2024, Volume and Issue: 69(12), P. 1866 - 1874

Published: April 16, 2024

Language: Английский

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Bromine radical enhanced stoichiometric pyridylation of alkylarenes and diarylmethanes at room temperature

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 10(4), P. 890 - 897

Published: Dec. 23, 2022

Sustainable photoredox catalysis with bromine radical-mediated hydrogen atom transfer enables stoichiometric pyridylation to synthesize a wide range of diarylmethanes and triarylmethanes in good excellent yields.

Language: Английский

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Photoredox‐catalyzed Decyanative Radical Cross‐coupling Reactions of Aromatic Nitriles

ChemCatChem, Journal Year: 2023, Volume and Issue: 16(5)

Published: Nov. 27, 2023

Abstract (Hetero)arenes are one kind of important structural motifs existed extensively in clinical pharmaceutics, pesticides, and so on. Developing novel method for introducing (hetero)aryl group through the employment cheap abundant feedstocks has attracted considerable attentions from synthetic community. In this review, we summarize recent advancements photoredox‐catalyzed decyanative cross‐coupling reactions based on persistent aromatic nitrile‐derived radical. We separate review into redox‐neutral reductive according to whether an external reducing agent is required. The diverse strategies overcoming redox potential limitation photocatalyst emphasized discussion specific reaction.

Language: Английский

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Ring-Opening α,β-Difunctionalization of Cyclopropanols with Azides Enables 4-Keto-Functionalized 1,2,3-Triazole Synthesis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9553 - 9557

Published: Oct. 28, 2024

Selective C–C bond cleavage and transformation of organic small molecules to create products increased value are one the central goals in chemistry. In this study, we have developed a novel TEMPO-mediated ring-opening α,β-difunctionalization cyclopropyl alcohols with azides prepare structurally important 4-keto-1,2,3-triazoles under metal- additive-free conditions. This protocol not only provides straightforward efficient method for synthesis 4-keto-functionalized 1,2,3-triazoles pot but also accomplishes goal constructing α,β-double C–N bonds via ring opening first time. Additionally, application skeletons drugs natural Kv1.5 channel blocker 4u further demonstrate synthetic potential practicability strategy.

Language: Английский

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Deoxygenative coupling of alcohols with aromatic nitriles enabled by direct visible light excitation

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(47), P. 9316 - 9320

Published: Jan. 1, 2023

A general and practical protocol is presented for visible-light-driven deoxygenative coupling of alcohols with aromatic nitriles in the absence external photocatalysts. Utilizing a hydroxyl activation strategy carbon disulfide, this C(sp3)-C(sp2) constructing platform accommodates broad scope aryl to deliver various alkyl-substituted arenes. Mechanism studies show that single electron transfer event between photoexcited nitrile xanthate anion key transformation.

Language: Английский

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Photocatalytic 1,3-Oxyheteroarylation of Aryl Cyclopropanes with Azine N-oxides

Chemical Science, Journal Year: 2024, Volume and Issue: 15(48), P. 20433 - 20439

Published: Jan. 1, 2024

Developed a difunctionalization method for aryl cyclopropanes using azine N -oxides as bifunctional reagents, generating β-heteroaryl ketones. This enables the use of previously challenging electron-deficient cyclopropanes.

Language: Английский

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Lewis Acid-Catalyzed Remote Site-Selective Ring Deconstruction of Cyclobuteno[a]naphthalene-4-ones to Access Unsymmetric 1,1-Diarylated Olefins

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3615 - 3625

Published: March 1, 2023

A catalytic site-selective ring deconstruction of cyclobuteno[a]naphthalene-4-ones with alcohols is reported, enabling the direct production a wide range unsymmetric 1,1-diarylated olefins good yields and complete regioselectivity. The late-stage application these resulting terminal demonstrates great possibilities to apply this strategy complex molecules. protocol features functional group compatibility, broad substrate scope, controllable site selectivity.

Language: Английский

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