Metallaphotoredox-enabled aminocarboxylation of alkenes with CO2

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(10), P. 959 - 968

Published: Sept. 21, 2023

Language: Английский

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Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(4), P. 398 - 462

Published: Jan. 18, 2023

Abstract The difunctionalizative trifluoromethylation of unsaturated C−C bonds is a highly useful and efficient method for the synthesis trifluoromethyl compounds with attractive architectures from simple feedstocks, allowing introduction CF 3 group along wide variety substituents either inter‐ or intramolecularly. Given that molecules are increasingly used as promising bioactive species in design new drugs agrochemicals, has been extensively studied during last decade. This review focuses on reactions proceeding via simultaneous formation C−heteroatom (O, N, S, Se, B) C−H bonds, these provide group‐containing building blocks. To identify trends prospects evolution this methodology, we systematically describe variants types more general view reaction conditions, modes, mechanisms. presented comprehensive survey enables categorization into those synthetically mature room further development. magnified image

Language: Английский

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Radical Decyanations of Unactivated Carbon‐CN Bonds: Recent Achievements and Mechanistic Studies

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(13), P. 2058 - 2091

Published: May 17, 2023

Abstract Decyanation is an important process in the synthesis of aromatic molecules studies pharmaceutical research, medical and materials sciences. In late‐stage modifications privileged carbo/heterocyclic scaffolds, radical‐type decyanation techniques have been devised to date. As a result, chemistry cyano‐involved conversions, hotly debated subject over past few decades, has advanced significantly. The cyano group (CN), on other hand, rarely acknowledged as good reaction site due its thermodynamic robustness. most recent advancements catalytic radical protocols that CN behaved leaving made are surveyed this article. Following introduction number different modes, reactions used activate C−CN bonds primarily categorized, text herein divided into three groups: (1) photo‐catalyzed transformations, (2) electro‐catalyzed (3) transition‐metal‐catalyzed or metal‐free transformations. With emphasis systems synthetic applications bond activation, review will provide readers with overview reactions.

Language: Английский

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Mediator-free electrochemical trifluoromethylation: a cascade approach for the synthesis of trifluoromethylated isoxazolines

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(30), P. 4467 - 4470

Published: Jan. 1, 2023

The developed methodology describes an environmentally benign protocol for electro-oxidative CF3-radical generation, followed by cascade cyclization fabricating isoxazoline scaffold from a β,γ-unsaturated oxime. Consecutive C-O and C-C bond formations were achieved through this method featuring mild, robust, scalable reaction conditions broad substrate scope. Mechanistic studies revealed the necessity of anodic oxidation process. Further conversion afforded other valuable derivatives.

Language: Английский

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Visible Light-Induced Decarbon-Carboxylation of Activated Alkenes by Carbon Dioxide

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1675 - 1675

Published: Jan. 1, 2024

An efficient visible light-facilitated decarbon-carboxylation of activated alkenes has been successfully developed.Compared with traditional alkene carboxylation, this method features mild conditions, up to 96% yield and good compatibility a variety functional groups.It provides new for the synthesis phenylacetic acid its derivatives.The mechanism study shows that reaction realizes corresponding carboxylic constant apparent carbon number by substituting carbon-carbon double bond alkene.Keywords light induction; dioxide; alkene; carboxylation 二氧化碳(CO 2 )作为丰富的可再生的 C1 合成子在合 成羧酸及其衍生物中备受关注 [1] , 其中, 芳基乙酸类化 合物有着显著的生物活性, 且部分已被开发为药物应用 于生活中(图 1) [2] .为此, 利用二氧化碳实现芳基苄位羧 化有着重要应用价值.在众多现有转化中, 存在底物复 杂、使用昂贵的过渡金属、反应条件苛刻、反应规模小、 反应废弃物多等不足, 所以, 发展绿色环保、反应条件 温和且无过渡金属参与的利用二氧化碳实现反应底物 的羧基化有着广阔的应用前景.以往的合成策略通常为 以下几种(Scheme 1a): (1)芳环苄位预留官能团后与二氧 化碳羧化获得目标产物 [3] .该类方法底物难直接获得, 原子经济性不高.(2)芳环苄位被攫氢或拔氢后与二氧化 碳反应 [4] .该策略往往因为攫氢效率低, C-H 选择性差 而未得到实际应用.(3)利用芳基烯烃与二氧化碳的氢羧 化 [5] 或者双官能团化反应 [6] 可以得到芳基乙酸类化合物.此类方法因其高效被化学家所青睐, 目前已发展出众多 方法, 包括烯烃的氢羧基化, 碳羧基化, 硫、硅、膦等杂 原子的羧基化.其中, 2020 年, Xi 等 [7] 报道了光催化的二 氧化碳和 N,N-二取代的芳胺参与的芳基烯烃的碳羧化 反应(Scheme 1b).该反应中, 三级胺既可以作为光氧化 还原反应中良好的还原剂, 同时也是氨基 α 位的碳自由 基前体试剂 [8] .在反应中本身被氧化成氨基自由基阳离 子, 经脱质子可以生成氨基 位的碳自由基物种.美中 不足的是, 在底物拓展方面, 作者仅考察了芳基烯烃都 有机化学

Language: Английский

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Cu-Electrocatalysis Enables Vicinal Bis(difluoromethylation) of Alkenes: Unraveling Dichotomous Role of Zn(CF₂H)₂(DMPU)₂ as Both Radical and Anion Source

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22498 - 22508

Published: July 30, 2024

The difluoromethyl group (CF2H) serves as an essential bioisostere in drug discovery campaigns according to Lipinski's Rule of 5 due its advantageous combination lipophilicity and hydrogen bonding ability, thereby improving the ADME properties. However, despite high prevalence importance vicinal bond donors pharmaceutical agents, a general synthetic method for doubly difluoromethylated compounds position is absent. Here we describe copper-electrocatalyzed strategy that enables bis(difluoromethylation) alkenes. By leveraging electrochemistry oxidize Zn(CF2H)2(DMPU)2-a conventionally utilized anionic transmetalating source, paved way utilize it CF2H radical source deliver terminal Mechanistic studies revealed interception resultant secondary by copper catalyst subsequent reductive elimination facilitated invoking Cu(III) intermediate, enabling second installation internal position. utility this electrocatalytic 1,2-bis(difluoromethylation) has been highlighted through late-stage bioisosteric replacement agents such sotalol dipivefrine.

Language: Английский

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Recent advances in the application of Langlois’ reagent in olefin difunctionalization

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(10), P. 2046 - 2058

Published: Nov. 18, 2022

This review describes several key activation methods for Langlois' reagent in the difunctionalization of alkenes and could stimulate interest readers promoting wider development application reagent.

Language: Английский

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Programmable synthesis of difluorinated hydrocarbons from alkenes through a photocatalytic linchpin strategy

Chemical Science, Journal Year: 2023, Volume and Issue: 14(41), P. 11546 - 11553

Published: Jan. 1, 2023

The introduction of difluoromethylene moieties into organic molecules has garnered significant attention due to their profound influence on the physicochemical and biological properties compounds. Nonetheless, existing approaches for accessing difluoroalkanes from readily available feedstock chemicals remain limited. In this study, we present an efficient modular protocol synthesis difluorinated compounds alkenes, employing accessible reagent, ClCF2SO2Na, as a versatile "difluoromethylene" linchpin. By means organophotoredox-catalysed hydrochlorodifluoromethylation followed by ligated boryl radical-facilitated halogen atom transfer (XAT) process, have successfully obtained various compounds, including gem-difluoroalkanes, gem-difluoroalkenes, difluoromethyl alkanes, with satisfactory yields. practical utility linchpin strategy been demonstrated through successful preparation CF2-linked derivatives complex drugs natural products. This method opens up new avenues structurally diverse hydrocarbons highlights radicals in organofluorine chemistry.

Language: Английский

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Photoredox-Catalyzed and Silane-Mediated Hydrofluoromethylation of Unactivated Alkenes with Fluoroiodomethane in Water

Organic Letters, Journal Year: 2023, Volume and Issue: 25(6), P. 1035 - 1039

Published: Feb. 7, 2023

The first hydrofluoromethylation of unactivated alkenes with fluoroiodomethane and hydrosilanes is developed by merging photoredox catalysis silane-mediated deiodination processes. key to the success this reaction use water as solvent enhance activity CH2F radical toward alkenes.

Language: Английский

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Acylmonofluoromethylation of alkenes via dual NHC/photoredox catalysis

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(24), P. 6124 - 6130

Published: Jan. 1, 2023

We herein describe a three-component radical acylmonofluoromethylation of alkenes by cooperative NHC/photoredox catalysis to synthesize various monofluorinated alkyl aryl ketones.

Language: Английский

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