The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10258 - 10271
Опубликована: Июль 11, 2024
Dearomatization is a fundamental chemical reaction that affords complex three-dimensional heterocyclic frameworks. We disclose the first organocatalytic dearomatization of 5-aminopyrazoles, which yields range structurally diversified C4-hydroxylated pyrazolines with ≤95% in <1.5 h at room temperature. This catalytic process achieved using
Язык: Английский
Science, Год журнала: 2024, Номер 386(6717), С. 99 - 105
Опубликована: Окт. 3, 2024
The identity of a heteroatom within an aromatic ring influences the chemical properties that heterocyclic compound. Systematically evaluating effect single atom, however, poses synthetic challenges, primarily as result thermodynamic mismatches in atomic exchange processes. We present photocatalytic strategy swaps oxygen atom furan with nitrogen group, directly converting into pyrrole analog intermolecular reaction. High compatibility was observed various derivatives and nucleophiles commonly used drug discovery, late-stage functionalization furnished otherwise difficult-to-access pyrroles from naturally occurring furans high molecular complexity. Mechanistic analysis suggested polarity inversion through electron transfer initiates redox-neutral processes at room temperature.
Язык: Английский
Процитировано
19
Chemical Society Reviews, Год журнала: 2024, Номер 53(12), С. 6600 - 6624
Опубликована: Янв. 1, 2024
Dearomatization has emerged as a powerful tool for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field evolved beyond simple dearomatization driven by new synthetic technology development. With the renaissance photocatalysis expansion activation mode, last few years have witnessed impressive developments in innovative photochemical methodologies, enabling skeletal modifications dearomatized structures. They offer truly efficient useful tools facile highly complex structures, which are viable natural product synthesis drug discovery. In this review, we aim to provide mechanistically insightful overview on these innovations based degree alteration, categorized into dearomative functionalization editing, highlight their utilities.
Язык: Английский
Процитировано
14
ACS Sustainable Chemistry & Engineering, Год журнала: 2023, Номер 11(35), С. 13142 - 13148
Опубликована: Авг. 24, 2023
Benzothiazolines, with their versatile nature, serve as fundamental building blocks for the synthesis of significant biological compounds. However, methods preparation benzothiazolines from readily available starting materials are limited. An efficient benzothiazoline via photoredox-catalyzed dearomatization benzothiazole derivatives has been achieved at room temperature. This catalysis proceeds a ligand to metal charge transfer process, and FeCl3 plays dual role an indirect HAT reagent reducing agent. methodology can be conveniently scaled up, most alkylated products purified without chromatography. In addition, this process exhibited advantages low cost, high reaction efficiency, mild conditions.
Язык: Английский
Процитировано
12
The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Фев. 18, 2025
A hexafluoroisopropanol (HFIP)-promoted hydrodifluoroalkylation of furans and vinyl ethers with difluorinated silyl enol has been developed. Because the inherent electron richer nature poor nucleophilicity ethers, employment simple as substrates for nucleophilic dearomatization without a metal or stoichiometric chemical oxidizing reagent is challenging, especially considering rearomatization driving force ring fragmentation furan system. This protocol exploits formation oxocarbenium intermediate from using HFIP proton source to allow addition which provides an efficient synthetic strategy install gem-difluorinated group into heterocycles.
Язык: Английский
Процитировано
0
ACS Sustainable Chemistry & Engineering, Год журнала: 2025, Номер unknown
Опубликована: Май 16, 2025
Язык: Английский
Процитировано
0
Asian Journal of Organic Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Май 28, 2025
Abstract Dearomatization offers an efficient strategy for directly converting arenes into cyclic molecules. In this review, we discuss representative examples of dearomatization reactions through five modes: (1) radical dearomatization, (2) halofunctionalization‐dearomatization, in which three‐membered intermediates were frequently involved, (3) nucleophilic mainly about electron‐rich arenes, (4) oxidative and (5) reductive dearomatization. Compared to heteroarenes, simple benzene are more challenging participate reactions. recent years, fewer reports have focused on benzene. Heteroarenes, inherently or easily activated, tend undergo readily. This review highlights a decade progress including indoles, benzofurans, benzothiophenes, thiophenes, furans, naphthols, naphthalenes, quinolines, pyridines, nitrobenzenes, benzenes. It also analyzes their mechanisms strategies. We hope will aid future research field.
Язык: Английский
Процитировано
0
Chinese Chemical Letters, Год журнала: 2023, Номер 35(4), С. 108902 - 108902
Опубликована: Авг. 9, 2023
Язык: Английский
Процитировано
7
Опубликована: Июнь 25, 2024
The direct coupling of alkene feedstocks with aldehydes represents an expedient approach to the generation new and structurally diverse C(sp3)-hybridized alcohols that are primed for elaborated into privileged architectures. Despite their abundance, current disconnection strategies enabling carbon-carbon π-bonds remain challenging because contemporary methods often limited by substrate or functional group tolerance, compatibility in complex molecular environments. Here, we report a between simple alkenes, heteroarenes unactivated aliphatic via electrochemically induced reductive activation C–C π bonds. cornerstone this is discovery rapid alternating polarity (rAP) electrolysis access direct, highly reactive radical anion intermediates derived from conjugated alkenes heterocyclic compounds. Our developed catalyst-free protocol enables new, alcohol products. This achieved controlled reduction C2–C3 π-bond unprecedented dearomative functionalization Experimental mechanistic studies demonstrate rAP necessary promotes kinetically biased single-electron over aldehydes. Overall, technology provides versatile olefin heterocycle aldehydes, offering straightforward C(sp3)-rich oxygenated scaffolds.
Язык: Английский
Процитировано
1
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(43), С. 29450 - 29461
Опубликована: Окт. 17, 2024
The direct coupling of alkene feedstocks with aldehydes represents an expedient approach to the generation new and structurally diverse C(sp3)-hybridized alcohols that are primed for elaboration into privileged architectures. Despite their abundance, current disconnection strategies enabling carbon–carbon π-bonds remain challenging because contemporary methods often limited by substrate or functional group tolerance compatibility in complex molecular environments. Here, we report a between simple alkenes, heteroarenes unactivated aliphatic via electrochemically induced reductive activation C–C π-bonds. cornerstone this is discovery rapid alternating polarity (rAP) electrolysis access highly reactive radical anion intermediates derived from conjugated alkenes heterocyclic compounds. Our developed catalyst-free protocol enables alcohol products. This achieved controlled reduction C2–C3 π-bond unprecedented dearomative functionalization Experimental mechanistic studies demonstrate kinetically biased single-electron over aldehydes. Application rAP chemoselective olefinic avoids undesired saturative overreduction. Overall, technology provides versatile olefin heterocycle aldehydes, offering straightforward C(sp3)-rich oxygenated scaffolds.
Язык: Английский
Процитировано
1
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10258 - 10271
Опубликована: Июль 11, 2024
Dearomatization is a fundamental chemical reaction that affords complex three-dimensional heterocyclic frameworks. We disclose the first organocatalytic dearomatization of 5-aminopyrazoles, which yields range structurally diversified C4-hydroxylated pyrazolines with ≤95% in <1.5 h at room temperature. This catalytic process achieved using
Язык: Английский
Процитировано
0