Three-Component Photochemical 1,2,5-Trifunctionalizations of Alkenes toward Densely Functionalized Lynchpins

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(43), С. 23814 - 23823

Опубликована: Окт. 18, 2023

Radical remote 1,n-difunctionalization reactions (n > 2) of alkenes are powerful tools to efficiently introduce functional groups with selected distances into target molecules. Among these reactions, 1,5-difunctionalizations an important subclass, leading sought-after scaffolds, but typically suffer from tailored starting materials and strict limitations for the formed group in 2-position. Seeking address issues make radical more applicable, we report a novel three-component 1,2,5-trifunctionalization reaction between imine-based bifunctional reagents two distinct alkenes, driven by visible light energy transfer-catalysis. Key achieving this selective one-step installation three different via choreographed formation four bonds was utilization 1,2-boron shift rigorous capitalization polarities stabilities. Thorough mechanistic studies were carried out, synthetic utility obtained products demonstrated various downstream modifications. Notably, addition functionalization individual groups, their interplay gave rise unique array cyclic products.

Язык: Английский

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Recent progress in the organoselenium-catalyzed difunctionalization of alkenes

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Язык: Английский

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Electrochemical Difunctionalization of Alkenes

The Chemical Record, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

Abstract Owing to their wide utilizations in synthesis and products prevalence numerous natural products, pharmaceuticals functional materials, the alkene difunctionalization methods for selective transformations of olefins are important have attracted much attention form synthetic chemists. Among them, electrochemical reaction is particularly promising has becoming a potent sustainable tool alkenes into vicinal difunctionalized structures organic through simultaneous incorporation two groups. Herein, we summarize recent progress reactions according types as well category radicals over past five years. By selecting remarkable examples, elaborately discussed substrate scope mechanisms olefin reaction.

Язык: Английский

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Radical-mediated alkoxypolyhaloalkylation of styrenes with polyhaloalkanes and alcohols via C(sp³)–H bond cleavage

Chemical Communications, Год журнала: 2021, Номер 57(30), С. 3684 - 3687

Опубликована: Янв. 1, 2021

A radical-mediated alkoxypolyhaloalkylation of styrenes with polychloroalkanes and alcohols for the facile synthesis complex polyhaloalkanes excellent functional-group compatibility a broad substrate scope.

Язык: Английский

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1,2-Amino oxygenation of alkenes with hydrogen evolution reaction

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Июль 30, 2022

Abstract 1,2-Amino oxygenation of alkenes has emerged as one the most straightforward synthetic methods to produce β-amino alcohols, which are important organic building blocks. Thus, a practical strategy for 1,2-amino is highly desirable. Here, we reported an electro-oxidative intermolecular with hydrogen evolution, removing requirement extra-oxidant. Using commercial oxygen and nitrogen sources starting materials, this method provides cheap, scalable, efficient route set valuable alcohol derivatives. Moreover, merit protocol been exhibited by its broad substrate scope good application in continuous-flow reactors. Furthermore, can be extended other amino-functionalization alkenes, thereby showing potential inspire advances applications electro-induced N -centered radicals (NCRs).

Язык: Английский

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Recent advances in the synthesis of 2,3-fused quinazolinones

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(32), С. 6293 - 6313

Опубликована: Янв. 1, 2022

As one of the most important structural units in pharmaceuticals and medicinal chemistry, quinazolinone its derivatives exhibit a wide range biological pharmacological activities, including anti-inflammatory, antitubercular, antiviral, anticancer etc. In particular, 2,3-fused quinazolinones have attracted much attention because rings fused to 2,3-positions improve their rigidity planarity. Their synthetic strategies made great advances recent years. Therefore, this review focuses on novel for synthesis from 2017 2022, such as difunctionalization alkenes, ring-opening easily available small rings, dehydrogenative cross-coupling reactions, transition-metal catalyzed cyclizations, cycloadditions, other cascade reactions.

Язык: Английский

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Electrochemical Difunctionalization of Alkenes

Synthesis, Год журнала: 2023, Номер 55(18), С. 2843 - 2859

Опубликована: Фев. 15, 2023

Abstract The electrochemical alkene difunctionalization reaction has become a powerful and sustainable tool for the efficient construction of vicinal difunctionalized structures in organic synthesis. Since only electrons are used as redox agents, avoids need additional catalysts, metal or chemical oxidants does not generate waste. Herein we summarize latest contributions alkenes over last 3–4 years. We discuss detail features, scope, limitations, mechanistic rationalizations three categories methods: (1) terminated by nucleophiles, (2) radicals, (3) functionality migration. 1 Introduction 2 Electrochemical Alkene Difunctionalization Terminated Nucleophiles 2.1 Sulfonylative Alkenes 2.2 Sulfurizative/Sulfoxidative 2.3 Azidotetrazolation 2.4 Trifluoromethylative 2.5 Diarylation 3 Radicals 3.1 Direct Radical-Coupling-Enabled 3.2 Metal-Mediated Radical Transfer Coupling Enabled 3.3 Metalloid-Mediated 4 Functionality Migration 5 Summary Outlook

Язык: Английский

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Recent Advances in Visible‐Light‐Driven C−S Bond Formation

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(20), С. 3413 - 3431

Опубликована: Сен. 12, 2023

Abstract Due their multifaced applications, the access to organosulfur derivatives in an efficient and economical way is a challenge organic synthesis. In this context photochemistry photocatalysis play crucial role development of innovative (and selective) Carbon‐Sulphur bond formation processes. The present review aims collect most recent strategies achieve target under visible light driven conditions.

Язык: Английский

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Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Molecules, Год журнала: 2023, Номер 28(7), С. 3027 - 3027

Опубликована: Март 28, 2023

Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction functional groups. In radical difunctionalization reactions, radicals first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, ring opening. The resulting undertake following paths second functionalization: (1) couple with other groups, (2) oxidize to cations then react nucleophiles, (3) reduce anions electrophiles, (4) metal-complexes. rearrangements provide opportunity 1,3-, 1,4-, 1,5-, 1,6-, 1,7-difunctionalization products. Multiple ways initiate reaction coupling intermediate make reactions good at remote positions. These offer advantages synthetic efficiency, operation simplicity, product diversity.

Язык: Английский

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Enantioselective Ni‐Catalyzed Three‐Component Dicarbofunctionalization of Alkenes

ChemCatChem, Год журнала: 2023, Номер 15(18)

Опубликована: Авг. 3, 2023

Abstract Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization alkenes has been well developed in recent years, which is used the area total synthesis natural products late‐stage modification drugs rapid incorporation sp 3 ‐enriched carbon centers. In this concept, significant breakthroughs field summarized, together with related mechanisms. Moreover, remaining challenges potential opportunities also highlighted.

Язык: Английский

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