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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An overview of chemo- and site-selectivity aspects in the chemical conjugation of proteins

Royal Society Open Science, Journal Year: 2022, Volume and Issue: 9(1)

Published: Jan. 1, 2022

The bioconjugation of proteins-that is, the creation a covalent link between protein and any other molecule-has been studied for decades, partly because numerous applications conjugates, but also due to technical challenge it represents. Indeed, proteins possess inner physico-chemical properties-they are sensitive polynucleophilic macromolecules-that make them complex substrates in conjugation reactions. This complexity arises from mild conditions imposed by their sensitivity selectivity issues, viz precise control site on protein. After decades research, strategies reagents have developed address two aspects this selectivity: chemoselectivity-harnessing reacting chemical functionality-and site-selectivity-controlling amino acid residue-most notably thanks participation synthetic chemistry effort. review offers an overview these strategies, insisting those employing native as substrates, shows that field is active exciting, especially chemists seeking new challenges.

Language: Английский

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Recent progress in alkynylation with hypervalent iodine reagents

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(12), P. 1589 - 1604

Published: Jan. 1, 2023

Although alkynes are one of the smallest functional groups, they among most versatile building blocks for organic chemistry, with applications ranging from biochemistry to material sciences. Alkynylation reactions have traditionally relied on use acetylenes as nucleophiles. The discovery and development ethynyl hypervalent iodine reagents allowed greatly expand transfer electrophilic synthons. In this feature article progress in field since 2018 will be presented. After a short introduction alkynylation reagents, developments synthesis alkynyl discussed. Their recent base-mediated transition-metal catalyzed alkynylations described. Progress radical-based atom-economical transformations then

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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Late-stage modification of bioactive compounds: Improving druggability through efficient molecular editing

Acta Pharmaceutica Sinica B, Journal Year: 2023, Volume and Issue: 14(3), P. 1030 - 1076

Published: Nov. 18, 2023

Synthetic chemistry plays an indispensable role in drug discovery, contributing to hit compounds identification, lead optimization, candidate drugs preparation, and so on. As Nobel Prize laureate James Black emphasized, "the most fruitful basis for the discovery of a new is start with old drug"

Language: Английский

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Dibenzothiophenium Salts: Practical Alternatives to Hypervalent I(III)-Based Reagents

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

ConspectusDuring the past few years, interest among organic synthesis practitioners in use of sulfonium salts has exponentially growth. This can arguably be attributed to a series specific factors: (a) The recent development more direct and efficient protocols for these species, which make reagents wide structural variety easily available multigram scale. (b) recognition that reactivity resembles hypervalent iodine compounds, therefore, they used as effective replacement such species most their applications. (c) Their intrinsic thermal stability tolerance air moisture, clearly surpass I(III)-reagents analogue reactivity, facilitate purification, isolation well-defined storage, safely handling on larger (d) Finally, possibility further functionalize once sulfur-containing platform been incorporated. Specifically, this last synthetic approach is not trivial when working with I(III)-species facilitates access no counterpart I(III) realm.This renewed led improvement already existing transformations well discovery unprecedented ones; particular, by incorporate partners traditional cross-coupling C–H activation steps or combine them modern technologies photocatalysis electrosynthesis. In Account, originally prepared our laboratory will outlined compared I(III)-counterparts. Some are now commercially available, started spread widely across chemistry community, helping speed process identification potentially bioactive products new functionaliced materials. However, challenges still remain. characterized an optimal balance between site-selectivity, showing broader compatibility toward sensitive functional groups need. addition, often makes necessary (sophisticated) catalysts activate latent hidden structures. Although priori one see fact disadvantage, it might actually decisive harvest full potential because surely preparation operational context I(III)-chemistry. If becomes true, may contribute expediting retrosynthetic disconnections that, date, impossible.

Language: Английский

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Hypervalent Iodine‐Mediated Late‐Stage Peptide and Protein Functionalization

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(7)

Published: Oct. 21, 2021

Hypervalent iodine compounds are powerful reagents for the development of novel transformations. As they exhibit low toxicity, high functional group tolerance, and stability in biocompatible media, have been used functionalization biomolecules. Herein, we report recent advances up to June 2021 peptide protein modification using hypervalent reagents. Their use as transfer or oxidizing is discussed this Minireview, including methods targeting polar, aromatic, aliphatic amino acids termini.

Language: Английский

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Fast Cysteine Bioconjugation Chemistry

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(66)

Published: Aug. 16, 2022

Cysteine bioconjugation serves as a powerful tool in biological research and has been widely used for chemical modification of proteins, constructing antibody-drug conjugates, enabling cell imaging studies. conjugation reactions with fast kinetics exquisite selectivity have under heavy pursuit they would allow clean protein just stoichiometric amounts reagents, which minimizes side reactions, simplifies purification broadens functional group tolerance. In this concept, we summarize the recent advances cysteine bioconjugation, discuss mechanism principles that underlie high efficiencies newly developed reactive reagents.

Language: Английский

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Chemical technology principles for selective bioconjugation of proteins and antibodies

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 380 - 449

Published: Dec. 14, 2023

Proteins are multifunctional large organic compounds that constitute an essential component of a living system. Hence, control over their bioconjugation impacts science at the chemistry-biology-medicine interface. A chemical toolbox for precision engineering can boost healthcare and open gateway directed or therapeutics. Such remained elusive long time due to complexity presented by pool functional groups. The precise single-site modification protein requires method address combination selectivity attributes. This review focuses on guiding principles segregate them simplify task method. disintegration systematically employs multi-step transformation deconvolute challenges. It constitutes disintegrate (DIN) theory offers additional parameters tuning in bioconjugation. outlines hurdles faced methods. elaborates developments perspective DIN demonstrate simultaneous regulation reactivity, chemoselectivity, site-selectivity, modularity, residue specificity, specificity. discusses progress such methods construct antibody conjugates biologics, including antibody-fluorophore antibody-drug (AFCs ADCs). also briefs how this knowledge assist developing small molecule-based covalent inhibitors. In process, it highlights opportunity hypothesis-driven routes accelerate discoveries selective establish new targetome proteins antibodies.

Language: Английский

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Merging Copper(I) Photoredox Catalysis and Iodine(III) Chemistry for the Oxy‐monofluoromethylation of Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 24, 2023

A simple process for the oxy-monofluoromethylation of alkenes is described. In combination with visible-light copper(I) photoredox catalysis, an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands serves as a powerful source monofluoromethyl (CH2 F) radical, enabling step economical synthesis γ-fluoro-acetates from broad range olefinic substrates under mild conditions. Applications to late-stage diversification derived complex molecules, amino acids and fluoromethylated heterocycles are also demonstrated.

Language: Английский

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