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

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

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

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Deconjugative Photoisomerization of Cyclic Enones

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

The deconjugative isomerization of α,β-unsaturated carbonyl compounds enables regioisomeric products to be forged with simultaneous Umpolung alkene reactivity. Although highly enabling, the endergonic nature net process coupled governing regioselectivity outcomes, renders it challenging. Innovations in positional linear species, often by light-triggered activation, have re-energized this area. However, cyclic enones is underdeveloped and associated impractical reaction conditions, limited substrate scopes, a lack mechanistic clarity. Herein, we report an operationally simple photochemical using near-UV (372 nm) irradiation catalytic amounts Brønsted acid (HCl). This platform exocyclic diverse array including α-isophorone (a key intermediate variety industrial processes), terpenoids steroids. Mechanistic studies reveal pivotal role solvent as mediator isomerization, where sequential hydrogen atom transfer (HAT) reverse-HAT (RHAT) are proposed operational.

Language: Английский

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Study of phenoxy radical couplings using the enzymatic secretome of Botrytis cinerea

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: May 28, 2024

Phenoxy radical coupling reactions are widely used in nature for the synthesis of complex molecules such as lignin. Their use laboratory has great potential production high value compounds from polyphenol family. While enzymes responsible generation radicals well known, behavior latter is still enigmatic and difficult to control a reaction flask. Previous work our using enzymatic secretome B. cinerea containing laccases shown that incubation stilbenes leads dimers, while phenylpropanoids dimers larger products. Building on these previous studies, this paper investigates role different structural features phenoxy couplings. We first demonstrate presence an exocyclic conjugated double bond plays efficient reactions. In addition, we show formation phenylpropanoid trimers tetramers can proceed via decarboxylation regenerates reactive moiety. Lastly, study reactivity other phenolic compounds: stilbene dihydro-stilbene, 4- O -methyl-stilbene simple phenol with . The observed dimerization consistently correlate para-phenol bond. absence feature variable results, some showing low conversion or no at all. This research allowed development controlled method specific derivatives novel derivatives, understanding promote

Language: Английский

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Base-assisted activation of phenols in TiO2 surface complex under visible light irradiation

Journal of Photochemistry and Photobiology A Chemistry, Journal Year: 2022, Volume and Issue: 431, P. 114005 - 114005

Published: May 10, 2022

Language: Английский

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One-pot access to sulfonylated naphthalenediols/hydroquinones from naphthols/phenols with sodium sulfinates in an aqueous medium

New Journal of Chemistry, Journal Year: 2020, Volume and Issue: 45(2), P. 610 - 614

Published: Dec. 8, 2020

A metal-free method towards sulfonylated hydroquinones/naphthalenediols under an ambient atmosphere has been developed with up to 97% yield.

Language: Английский

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Visible-light-promoted generation of p-(N,N-dimethyl)benzyl equivalents and their reactions with quinols: easy access to diarylalkanes

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(4), P. 859 - 865

Published: Jan. 1, 2023

Highly-selective generation of p -( N , -dimethyl)benzyl equivalents from -dimethyl arylamines via α-amino alkyl radicals and their reactions with quinols for diarylalkane synthesis.

Language: Английский

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Blue‐LED Synthesis of Pummerer's Ketones by Peroxidase‐Lignin‐Catalyzed Oxidative Coupling of Substituted Phenols

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(32)

Published: June 30, 2023

Abstract Pummerer's ketones resembling the tricyclic scaffold of bioactive natural substances were synthesized by blue‐LED driven Horseradish Peroxidase oxidative coupling substituted phenols in 2‐methyltetrahydrofuran using meso ‐tetraphenylporphyrin as photosensitizer and dioxygen primary oxidant. The application functionalized lignin nanoparticles a renewable efficient platform for immobilization enzyme extended effectiveness overall process to heterogeneous catalysis under buffer limiting conditions.

Language: Английский

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Synthesis of substituted 2,2'- and 4,4'-biphenyldiols using oxidative coupling reaction

From Chemistry Towards Technology Step-By-Step, Journal Year: 2023, Volume and Issue: 4(4), P. 52 - 59

Published: Dec. 23, 2023

Based on the oxidative coupling reaction, methods for synthesis of substituted 2,2'- and 4,4'-biphenyldiols have been developed. These biphenyldiols were not described in literature. The article presents potential applications limitations method using potassium ferricyanide iron (III) chloride hexahydrate.

Language: Английский

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First Evidence of Pheomelanin-UVA-Driven Synthesis of Pummerer’s Ketones by Peroxidase-Mediated Oxidative Coupling of Substituted Phenols

ACS Omega, Journal Year: 2022, Volume and Issue: 7(49), P. 45688 - 45696

Published: Nov. 29, 2022

Photoexcitation of pheomelanin produces high-energy singlet oxygen and the superoxide anion, which are reactive species in damage cellular targets. In principle, these can be involved processes synthetic utility when adequate experimental conditions defined. Here, we describe that performs as a selective UVA antenna for horseradish peroxidase oxidative coupling substituted phenols to biologically active Pummerer's ketones under 2-methyltetrahydrofuran/buffer biphasic conditions. this system, is scavenged by conversion 2-methyltetrahydrofuran into corresponding organic hydroperoxide, while anion dismutated hydrogen peroxide. Both intermediates able oxidize site triggering reaction. Trimer derivatives, produced addition phenoxy radicals on preformed were also isolated, suggesting possibility further improve structural complexity reaction products.

Language: Английский

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PhIO-Mediated Oxidative C═C Bond Cleavage and Reassembly toward Highly Functionalized Oxazolones

Organic Letters, Journal Year: 2022, Volume and Issue: 24(6), P. 1323 - 1328

Published: Feb. 7, 2022

An efficient PhIO-mediated oxidative C═C bond cleavage and reassembly of enaminone toward oxazolone with high regioselectivity has been reported. DFT calculations revealed that the reaction proceeded through an oxygen atom transfer, cleavage, alkylthio migration, cascade. This strategy is highlighted by step economy formation five bonds in one pot generation a high-valued skeleton under mild conditions.

Language: Английский

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