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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Carboxylic Acid Directed γ-Lactonization of Unactivated Primary C–H Bonds Catalyzed by Mn Complexes: Application to Stereoselective Natural Product Diversification

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(42), P. 19542 - 19558

Published: Oct. 13, 2022

Reactions that enable selective functionalization of strong aliphatic C–H bonds open new synthetic paths to rapidly increase molecular complexity and expand chemical space. Particularly valuable are reactions where site-selectivity can be directed toward a specific bond by catalyst control. Herein we describe the catalytic site- stereoselective γ-lactonization unactivated primary in carboxylic acid substrates. The system relies on chiral Mn activates aqueous hydrogen peroxide promote intramolecular lactonization under mild conditions, via carboxylate binding metal center. exhibits high enables oxidation γ-C–H even presence intrinsically weaker priori more reactive secondary tertiary ones at α- β-carbons. With substrates bearing nonequivalent bonds, factors governing have been uncovered. Most remarkably, manipulating absolute chirality catalyst, methyl groups gem-dimethyl structural units rigid cyclic bicyclic acids achieved with unprecedented levels diastereoselectivity. Such control has successfully exploited late-stage natural products such as camphoric, camphanic, ketopinic, isoketopinic acids. DFT analysis points rebound type mechanism initiated 1,7-HAT from bound substrate highly MnIV-oxyl intermediate, deliver carbon radical lactonizes through transfer. Intramolecular kinetic deuterium isotope effect 18O labeling experiments provide support this mechanistic picture.

Language: Английский

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Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Organometallics, Journal Year: 2023, Volume and Issue: 42(18), P. 2598 - 2612

Published: March 1, 2023

The reaction of Ni(II) acetate with diacyl peroxides produces high-valence Ni-species capable catalytic oxidative acyloxylation C(sp3)–H bonds in ethers, ketones, and alkanes. desired esters were obtained 20–82% yields. Computational analysis suggests that activation the peroxide moiety a dynamically interconverting mixture formal Ni(III) state. Remarkably, these species, coordination RCO2 group at Ni preserves radical character carboxylate (i.e., acts as an “L-ligand”), so latter can induce fast C–H abstraction. spirocyclopropyl prevents premature decarboxylation via combination hybridization factors stereoelectronic effects. A variety viable patterns identified experimentally computationally.

Language: Английский

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Organocatalytic activation of hydrogen peroxide: towards green and sustainable oxidations

Chemical Science, Journal Year: 2023, Volume and Issue: 15(4), P. 1177 - 1203

Published: Dec. 18, 2023

The advent of organocatalysis provided an additional option in every researcher's arsenal, towards the development elegant and sustainable protocols for various organic transformations. Oxidation reactions are considered to be key synthesis since oxygenated functionalities appear many natural products. Hydrogen peroxide is categorized as a green oxidant, its only by-product water, offering novel opportunities protocols. In this review article, we intend present recent developments field organocatalytic activation hydrogen peroxide, providing useful insight into applied oxidative At same time, will some interesting mechanistic studies, information on oxygen transfer processes.

Language: Английский

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Photocatalytic Sulfonyl Peroxidation of Alkenes via Deamination of N-Sulfonyl Ketimines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1920 - 1925

Published: Feb. 22, 2024

A photocatalytic three-component sulfonyl peroxidation of alkenes with N-sulfonyl ketimines and tert-butyl hydroperoxide is reported. The reaction takes place via the photoinduced EnT process, which allows efficient synthesis a variety β-peroxyl sulfones under mild conditions in absence transition metal catalyst. downstream derivatizations peroxides were also performed. Furthermore, utility this protocol was manifested by 11β-HSD1 inhibitor antiprostate cancer drug bicalutamide.

Language: Английский

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1-Azahomocubane

Chemical Science, Journal Year: 2023, Volume and Issue: 14(11), P. 2821 - 2825

Published: Jan. 1, 2023

1-Azahomocubane has been prepared 56 years after the parent hydrocarbon. Introduction of a nitrogen atom into this constrained polycyclic environment resulted in minimal changes to framework geometry, with s-character lone pair increasing due strain.

Language: Английский

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Interrupted Dance of Five Heteroatoms: Reinventing Ozonolysis to Make Geminal Alkoxyhydroperoxides from C═N Bonds

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5699 - 5714

Published: April 2, 2024

Four heteroatoms dance in the cascade of four pericyclic reactions initiated by ozonolysis C═N bonds. Switching from imines to semicarbazones introduces fifth heteroatom that slows this dance, delays reaching thermodynamically favorable escape path, and allows efficient interception carbonyl oxides (Criegee intermediates, CIs) an external nucleophile. The new three-component reaction alcohols, ozone, oximes/semicarbazones greatly facilitates synthetic access monoperoxyacetals (alkoxyhydroperoxides).

Language: Английский

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Pd-Catalyzed C–O Bond Formation: Coupling of Aryl Boronic Acids with O-Electrophiles

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3636 - 3646

Published: Feb. 14, 2025

Language: Английский

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Oxygen: The Key to Stereoelectronic Control in Chemistry

ACS in focus, Journal Year: 2023, Volume and Issue: unknown

Published: April 4, 2023

Although carbon is considered the central element of organic chemistry, broader chemical world has one more star player—oxygen. Billions years evolution have filled your room with oxygen as countless cyanobacteria and plants work on changing our planet. Oxygen everywhere—from geology to biology, from Earth's crust ozone layer. This digital primer aims analyze reactivity through prism chemistry. The key understanding this chemistry lone pairs (i.e., underutilized "idle" electrons that do not directly contribute Lewis structure molecules). By highlighting many roles oxygen, we will illustrate how rises above limitations structures stay neither idle nor "lone" even if they are in "lone pairs" when an atom near a reaction center. introduce important types bonding transcend undergraduate textbooks but likely drive development new reactions future.

Language: Английский

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“Stereoelectronic Deprotection of Nitrogen”: Recovering Nucleophilicity with a Conformational Change

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 6868 - 6877

Published: May 22, 2023

Ureas are often thought of as "double amides" due to the obvious structural similarity these functional groups. The main feature an amide is its planarity, which responsible for conjugation between nitrogen atom and carbonyl moiety decrease nucleophilicity. Consequently, since amides poor nucleophiles, ureas nucleophiles well. Herein, we demonstrate that can be distinctly different from amides. These differences amplified by rotation around one ureas' C-N bonds, switches off resonance recovers nucleophilicity atoms. This conformational change further facilitated judicious introduction steric bulk disfavor planar conformation. in reactivity example "stereoelectronic deprotection," a concept when desired group produced rather than chemical modification. may used complementarily traditional protecting We also both viability utility this synthesis unusual 2-oxoimidazolium salts possessing quaternary atoms at urea moiety.

Language: Английский

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