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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Iodoarene Activation: Take a Leap Forward toward Green and Sustainable Transformations

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide is a crucial step most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling direct (hetero)arylation trapping reagents construction highly functionalized (hetero)arenes benign conditions. strategies for aryl iodides are classified into (a) hypervalent iodoarene followed by functionalization thermal/photochemical conditions, (b) aryl-I bond in presence bases with/without organic catalysts promoters, (c) photoinduced presence/absence organophotocatalysts, (d) electrochemical direct/indirect electrolysis mediated organocatalysts mediators acting as electron shuttles, (e) electrophotochemical redox-active organocatalysts. These modes result exhibiting diverse reactivity formal cations/radicals/anions aryne precursors. coupling these reactive intermediates with leads to facile selective formation C-C C-heteroatom bonds. ecofriendly, inexpensive, functional group-tolerant offer alternatives transition metal-based catalysis.

Language: Английский

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Preparation of seven-coordinated hypervalent tin(iv)-fused azobenzene and applications for stimuli-responsive π-conjugated polymer films

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(28), P. 11858 - 11866

Published: Jan. 1, 2024

Seven-coordinated hypervalent tin( iv ) compounds with large binding constants were prepared and applied for vapochromic thermochromic π-conjugated polymer films.

Language: Английский

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Utilization of Hypervalent Bonds as a Novel Strategy for Manipulating Energy Levels of π‐Conjugated Systems

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(45)

Published: Aug. 20, 2024

Abstract The unique optical properties created by the combination of azobenzene‐based π‐conjugated systems and hypervalent bonds are summarized. bond, a polarized three‐center four‐electron (3c−4e) simultaneously provides electron‐donating ‐withdrawing effects to directly attached system. resulting compounds have dramatically narrow energy gap showing near‐infrared (NIR) emission despite limited size systems. In addition, also exhibit stimuli‐responsive chromism through reversible coordination‐number shift central main‐group elements in both crystals polymer films. We explain that nature depends on element type, which is particularly effective bringing out heavy elements. this review, we describe use novel strategy not only for manipulating levels system but developing variety functional materials based newly rising from element.

Language: Английский

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Photocatalytic Regioselective Alkoxycarbonylation/Cyclization of 3-Aza-1,5-dienes: Access to Ester-Containing Pyrrolin-2-ones

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

Published: March 13, 2025

A direct alkoxycarbonyl radical-induced cascade reaction of 3-aza-1,5-dienes with alkyl chlorooxoacetates is reported. With this approach, an extensive range ester-containing pyrrolin-2-ones are synthesized through photocatalyzed alkoxycarbonylation/cyclization under mild conditions. Moreover, dehydrogenative aromatization can proceed the same photocatalytic system.

Language: Английский

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Benzothiazolines Acting as Carbanion and Radical Transfer Reagents in Carbon–Carbon Bond Construction

Molecules, Journal Year: 2025, Volume and Issue: 30(8), P. 1711 - 1711

Published: April 11, 2025

Traditionally employed as hydrogenation reagents, benzothiazolines have emerged versatile carbanion and radical transfer playing a vital role in the construction of various carbon-carbon bonds. The cutting-edge progress photochemistry chemistry prompted study visible light-driven reactions, bringing into vibrant focus. Their chemical processes been uncovered to encompass variety activation mechanisms, with five distinct modes having identified. This work reviews innovative applications donors alkyl or acyl groups, achieving hydroalkylation hydroacylation substitution. By examining their diverse this review highlights potential serving groups for further research development. Moreover, will offer exemplary inspiration synthetic chemists, contributing ongoing evolution utility organic synthesis.

Language: Английский

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Quadrupolar dinuclear hypervalent tin(iv) compounds with near-infrared emission consisting of Schiff bases based on π-conjugated scaffolds

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

Published: Jan. 1, 2024

Since π-conjugated molecules are commonly used as a scaffold for constructing optoelectronic and functional materials, much effort has been devoted to exploring novel molecular scaffolds obtaining superior properties. This study focuses on dinuclear hypervalent tin(iv) compounds prepared by the ladderization of Schiff bases using tin units. The optical measurements found that introducing atoms can reinforce D-π-A system. We synthesized two types simple condensation reactions observed near-infrared (NIR) emission. Also, depending direction imine bonds, these had different quadrupolar orientations with D-π-A-π-D A-π-D-π-A systems followed negative solvatochromism, which is unique behavior quadrupolar-derived absorption. Furthermore, polymers involving showed NIR emission in wavelength range over 800 nm owing distinct expansion π-conjugation. Our findings could be useful not only electronic structures narrow energy gaps but also designing states environmental responsiveness.

Language: Английский

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Stimuli‐Responsive Optical Materials Based on Hypervalent Antimony‐Containing Conjugated Molecules

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 17, 2024

Abstract Stimuli‐responsive materials have been applied for sensor devices because they can transform and amplify various target stimuli into observable signals. Much effort has devoted to exploring effective molecular designs obtaining stimuli‐responsive behaviors by taking advantage of the unique optoelectronic properties π‐conjugated molecules involving elements. This study focuses on modulation electronic state scaffolds oxidation number change hypervalent antimony. demonstrate that strength intramolecular interaction between antimony framework be tuned with ligand structure, substituent effect, shifts In particular, color changes represented hypsochromic bathochromic wavelength optical bands are achieved oxidative reaction in solid state. Significantly, direction confidently predicted quantum chemical calculations. The findings, based main‐group elements, provide logical design strategies advanced materials.

Language: Английский

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