The chemistry of heterocycles in the 21st century

Russian Chemical Reviews, Journal Year: 2024, Volume and Issue: 93(7), P. RCR5125 - RCR5125

Published: July 1, 2024

The chemistry of heterocyclic compounds has traditionally been and remains a bright area chemical science in Russia. This is due to the fact that many heterocycles find widest application. These are key structural fragments most drugs, plant protection agents. Many natural also derivatives heterocycles. At present, more than half hundreds millions known collective review devoted achievements Russian chemists this field over last 15–20 years. presents leading heterocyclists representing both RAS institutes university science. It worth noting wide scope review, terms geography author teams, covering whole our large country, diversity research areas. Practically all major types represented review. special attention focused on practical applications design new drugs biologically active compounds, high-energy molecules, materials for organic electronics photovoltaics, ligands coordination chemistry, other rapidly developing advances would not be possible without development fundamental transformations chemistry.<br> Bibliography — 2237 references.

Language: Английский

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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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Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 5938 - 5943

Published: Jan. 1, 2024

Cyclopropyl-substituted sulfonium salts are obtained by Rh-catalysed addition of α-diazo dibenzothiophenium to olefins. When indenes used as substrates, initially formed cyclopropyl rings open with concomitant elimination dibenzothiophene, enabling access 2-substituted naphthalenes.

Language: Английский

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Amino‐λ³‐iodane‐Enabled Electrophilic Amination of Arylboronic Acid Derivatives

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(12)

Published: Jan. 26, 2024

Abstract In this report, we describe the use of amino‐λ 3 ‐iodanes in electrophilic amination arylboronic acids and boronates. Iodine(III) reagents with transferable amino groups, including one an NH 2 group, were synthesized used amination, allowing synthesis a wide range primary secondary (hetero)arylamines. Mechanistic studies by DFT calculations indicate that reaction proceeds through process from tetravalent borate complex B−N dative bond.

Language: Английский

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Carboiodanation of Arynes: Organoiodine(III) Compounds as Nucleophilic Organometalloids

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3910 - 3919

Published: Feb. 5, 2024

Organic iodine(III) compounds represent the most widely used hypervalent halogen in organic synthesis, where they typically perform role of an electrophile or oxidant to functionalize electron-rich -nucleophilic compounds. In contrast this convention, we discovered their unique reactivity as organometallic-like nucleophiles toward arynes. Equipped with diverse transferable ligands and supported by a tethered spectator ligand, organoiodine(III) undergo addition across electrophilic C–C triple bond arynes while retaining trivalency iodine center. This carboiodanation reaction can forge variety aryl–alkynyl, aryl–alkenyl, aryl–(hetero)aryl bonds along concurrent formation aryl–iodine(III) under mild conditions. The newly formed serves versatile linchpin for downstream transformations, particularly site. amphoteric nature group metalloid leaving sequence enables flexible expedient synthesis extended π-conjugated molecules privileged biarylphosphine ligands, all iodine(III)-containing be handled air- thermally stable materials.

Language: Английский

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Organohypervalent heterocycles

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4786 - 4827

Published: Jan. 1, 2024

This review summarizes structural and synthetic aspects of heterocyclic molecules incorporating an atom a hypervalent main-group element. The higher thermal stability heterocycles, as compared to their acyclic analogs, adds special feature chemistry.

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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2,2‐Difluoroethylation of Heteroatom Nucleophiles via a Hypervalent Iodine Strategy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 8, 2024

The 2,2-difluoroethyl group is an important lipophilic hydrogen bond donor in medicinal chemistry, but its incorporation into small molecules often challenging. Herein, we demonstrate electrophilic 2,2-difluoroethylation of thiol, amine and alcohol nucleophiles with a hypervalent iodine reagent, (2,2-difluoro-ethyl)(aryl)iodonium triflate, via proposed ligand coupling mechanism. This transformation offers complementary strategy to existing methods allows access wide range 2,2-difluoroethylated nucleophiles, including the drugs Captopril, Normorphine Mefloquine.

Language: Английский

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Bond Strength and Interaction Energies in Togni Reagents: Insights from Molecular Electrostatic Potential-Based Parameters

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(4), P. 727 - 737

Published: Jan. 22, 2024

Togni reagents and their analogs, classified as hypervalent iodine(III) complexes, serve potent trifluoromethylation agents. The interplay of cis trans factors plays a pivotal role in shaping performance, affecting aspects such bond strength, interaction energies, stability, subsequent nucleophilic reactions. In this context, we propose the utilization molecular electrostatic potential (MESP) at carbon atom (VC) I–CF3 moiety sensitive parameter to quantify influences Togni-type reagents. Our study has shown that VC serves convenient probe for determining heterolytic dissociation energy (BDE) and, consequently, assessing reactivity these Moreover, parameters have been successfully applied evaluate strength σ-hole interactions with nucleophiles (Cl– NMe3). Additionally, provide insights into Brønsted acids HCl HSO3F, elucidating them terms MESP topological parameters. These findings yield valuable information about electronic properties iodine reagents, particularly offering optimizing structurally modified enhanced activity stability.

Language: Английский

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