Recent advances in transition metal-mediated trifluoromethylation reactions

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(75), P. 10442 - 10468

Published: Jan. 1, 2022

Fluorine compounds are known for their abundance in more than 20% of pharmaceutical and agrochemical products mainly due to the enhanced lipophilicity, metabolic stability pharmacokinetic properties organofluorides. Consequently, last decade has seen enormous growth incorporation a trifluoromethyl group into organic motifs. With significance, this review aims provide complete picture transition metal-mediated construction C(sp3, sp2, sp)-CF3 bonds via C-H/X bond functionalization or addition processes both aliphatic aromatic hydrocarbons. Diversified reagents ranging from radical electrophilic nucleophilic trifluoromethylating agents respective mechanisms have been further deliberated comprehensive overview. The coverage on topic is expected make unique beneficial future applications enriching community towards improvements field trifluoromethylation reactions, turn improving propensity development drugs.

Language: Английский

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Nickel-Catalyzed Modular Four-Component 1,4-Alkylcarbonylation of 1,3-Enynes to Tetra-Substituted CF₃–Allenyl Ketones

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2144 - 2150

Published: Jan. 25, 2024

The modular four-component carbonylation of unsaturated hydrocarbons represents an elegant strategy for the one-pot synthesis complex carbonyl compounds. However, this is currently focused on 1,2-difunctionalization olefins or alkynes, and 1,4-alkylcarbonylation 1,3-enynes remains unexplored. In study, we report a Ni-catalyzed CF3-containing under 1 atm CO, which affords tetra-substituted CF3-allenyl ketones with good yields selectivity. This protocol features mild conditions, broad substrate scope, acceptable functional group compatibility. Control experiments revealed that reactivity oxime esters (regulated by leaving groups) polarity matching are crucial success cascade. Preliminary mechanistic studies suggest acyl nickel key intermediate in transformation.

Language: Английский

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Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(16), P. 2653 - 2675

Published: April 21, 2023

Abstract Hypervalent iodine compounds have found broad application in modern organic chemistry as reagents and catalysts. Cyclic hypervalent based on the benziodoxole heterocyclic system higher stability compared to their acyclic analogues, which makes possible preparation safe handling of with special ligands such azido, cyano, trifluoromethyl groups. Numerous iodine‐substituted derivatives been prepared utilized for transfer substituent substrate. Reactions these substrates can be performed under metal‐free conditions, presence transition metal catalysts, or using photocatalysts photoirradiation conditions. In this review, we focus most recent synthetic applications cyclic iodine(III) following ligands: N 3 , NHR, CN, CF SCF OR, OAc, ONO 2 C(=N )CO R. The review covers literature published mainly last 5 years.

Language: Английский

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Nickel‐Catalyzed Four‐Component Carbonylation of Ethers and Olefins: Direct Access to γ‐Oxy Esters and Amides

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 13, 2022

Abstract Multi‐component carbonylation of olefins, a reaction that installs both carbon–carbon(heteroatom) bond and carbonyl group across the double bond, is an attractive strategy for alkene functionalization. Herein, we developed novel nickel‐catalyzed four‐component olefins with ethers under low CO gas pressure. Using alcohols amines as partner, diverse γ ‐oxy‐substituted esters amides were produced in good yields excellent functional tolerance. Notably, Naftidrofuryl, medicine treatment cerebrovascular disease (CVD), can be synthesized by this process straightforwardly.

Language: Английский

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Copper‐Catalyzed 1,2‐Dicarbonylative Cyclization of Alkenes with Alkyl Bromides via Radical Cascade Process

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Oct. 18, 2022

Herein, we developed a new procedure on 1,2-dicarbonylative cyclization of 4-aryl-1-butenes with alkyl bromides. Using simple copper catalyst, two molecules carbon monoxide were introduced into the double bond formation four C-C bonds and ring. Various α-tetralones 2,3-dihydroquinolin-4-ones formed in moderate to good yields.

Language: Английский

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Visible‐Light‐Driven Four‐Component Radical Relay Aminocarbonylation of Unactivated Alkenes^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(9), P. 990 - 996

Published: Jan. 18, 2024

Comprehensive Summary Catalytic four‐component radical carbonylation of unactivated alkenes has recently been recognized as a robust protocol for rapid construction various structurally diverse carbonyl compounds. Given the significance fluorine‐containing groups, this reaction class extensively applied to assembly variety perfluoroalkyl carboxylic acid derivatives by transition metal catalysis. Herein, we report visible‐light‐driven relay 1,2‐perfluoroalkylation aminocarbonylation using CO gas source and 4CzIPN organic photocatalyst. A wide range amines were well tolerated, providing valuable β‐perfluoroalkylated amides with generally good yields high chemoselectivity.

Language: Английский

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A straightforward access to trifluoromethylated natural products through late-stage functionalization

Natural Product Reports, Journal Year: 2022, Volume and Issue: 40(5), P. 988 - 1021

Published: Oct. 7, 2022

This review summarizes the applications of late-stage strategies in direct trifluoromethylation natural products past ten years, with particular emphasis on reaction model each method.

Language: Английский

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Dearomative Aminocarbonylation of Arenes via Bifunctional Coordination to Chromium

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 16, 2022

Abstract Amides are ubiquitous in physical and life sciences. Given the significant abundance of arenes, dearomative aminocarbonylation arenes would lead to a large underexplored chemical space for amide discovery. However, such reactions challenging due high degree resonance stabilization selectivity issues. Herein, we disclose an unprecedented trifluoromethylative via bifunctional coordination chromium, providing modular platform construction amides possessing trifluoromethyl (CF 3 ) groups three‐dimensional rings. Its versatility further enabled switchable difluoromethylation or trifluoromethylation arene C−H bonds. A possible mechanism was proposed based on control experiments. Finally, synthetic utility well demonstrated by diverse applications total synthesis CF ‐functionalized amide‐type drugs, including praziquantel, nateglinide, maraviroc alloyohimbane.

Language: Английский

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Visible-Light-Promoted Intermolecular β-Acyl Difunctionalization of Alkenes via Oxidative Radical-Polar Crossover

Organic Letters, Journal Year: 2023, Volume and Issue: 25(45), P. 8067 - 8071

Published: Nov. 8, 2023

A visible-light-induced β-acyl difunctionalization of alkenes with acyl oxime esters and various nucleophiles was developed to achieve molecular complexity from readily available raw materials via oxidative radical-polar crossover. variety nucleophiles, including NH-sulfoximines, indoles, indazole, trimethoxybenzene, were all effectively applicable the sustainable reaction system. The novel synthetic strategy features mild conditions, a broad substrate scope (39 examples), easy scale-up, excellent regioselectivity.

Language: Английский

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Cobalt-catalyzed aminoalkylative carbonylation of alkenes toward direct synthesis of γ-amino acid derivatives and peptides

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

Published: Nov. 17, 2023

Abstract γ-Amino acids and peptides analogues are common constituents of building blocks for numerous biologically active molecules, pharmaceuticals, natural products. In particular, γ-amino providing with better metabolic stability than α-amino acids. Herein we report a multicomponent carbonylation technology that combines readily available amides, alkenes, the feedstock gas carbon monoxide to build architecturally complex functionally diverse acid derivatives in single step by implementation radical relay catalysis. This transformation can also be used as late-stage functionalization strategy deliver complex, advanced products pharmaceutical other areas.

Language: Английский

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