Enantioselective Radical Reactions Using Chiral Catalysts

Chemical Reviews, Год журнала: 2022, Номер 122(6), С. 5842 - 5976

Опубликована: Янв. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Язык: Английский

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Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds

Chemical Society Reviews, Год журнала: 2022, Номер 51(7), С. 2759 - 2852

Опубликована: Янв. 1, 2022

C-H functionalization has been emerging as a powerful method to establish carbon-carbon and carbon-heteroatom bonds. Many efforts have devoted transition-metal-catalyzed direct transformations of Metal carbenes generated in situ from transition-metal compounds diazo or its equivalents are usually applied the transient reactive intermediates furnish catalytic cycle for new C-C C-X bond formation. Using this strategy unactivated simple alkanes complex molecules can be further functionalized transformed multi-functionalized compounds. In area, carbene insertion bonds paid continuous attention. Diverse catalyst design strategies, synthetic methods, potential applications developed. This critical review will summarize advance dated up July 2021, by categories aliphatic C(sp3)-H, aryl (aromatic) C(sp2)-H, heteroaryl (heteroaromatic) C(sp2)-H bonds, alkenyl alkynyl C(sp)-H, well asymmetric more coverage given recent work. Due rapid development future directions topic also discussed. give authors an overview chemistry with focus on systems

Язык: Английский

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Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3452 - 3506

Опубликована: Март 3, 2022

Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, they are high demand. This will be a cause concern, hence, it important to develop methods based 3d metals, which widely present Earth's crust. In this regard, metal catalysts or their precursors for catalysis, general, functionalizations, particular, has gained significant momentum The major development catalytic with been achieved predominantly strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, 8-amino-quinolinyl groups. Thus, prefunctionalization substrates these necessary, contradicts step- atom-economy activation. commonly available functional aldehyde, ketone, carboxylic acid, amide, hydroxy, N-oxides loosely bind through weak-coordination. These weakly orient activate regioselectively without need preinstalled Although challenging, contemporary topic actively pursued by many researchers Through article, we provide comprehensive overview metal-catalyzed, coordinating, directing-group-enabled reported until March 2021.

Язык: Английский

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Iron-catalysed reductive cross-coupling of glycosyl radicals for the stereoselective synthesis of C-glycosides

Nature Synthesis, Год журнала: 2022, Номер 1(3), С. 235 - 244

Опубликована: Фев. 17, 2022

Язык: Английский

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Challenges and recent advancements in the transformation of CO₂into carboxylic acids: straightforward assembly with homogeneous 3d metals

Chemical Society Reviews, Год журнала: 2022, Номер 51(22), С. 9371 - 9423

Опубликована: Янв. 1, 2022

The transformation of carbon dioxide (CO2) into useful chemicals, advanced materials, and energy is a long-standing challenge in both fundamental science industry. In recent years, utilization CO2 the presence inexpensive non-negligible environmentally friendly 3d metal-based catalysts (Fe, Mn, Co, Ni, Cu Ti) has become one most attractive topics. Particular attention been given to synthesis carboxylic acids their derivatives since these molecules serve as key intermediates chemical, fertilizer, pharmaceutical sectors. Considering numerous challenges linked with reactivity, number research groups have recently focused on by following thermo-, photo-, electrochemical strategies. However, facile access such remains vital catalysis organic owing high stability molecule which atom highest oxidation state. Another hurdle solve selectivity issue caused reaction different catalytic systems reactive functional group-containing molecules. Despite all issues, wide range transition applied this direction, but cheaper price inherent metals are at forefront domain. these, we aim summarise advances (over past five years) 3d-metal complexes reactivity towards activation for acids. Furthermore, discuss current trends, knowledge gaps, invigorating perspectives future advances.

Язык: Английский

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Current Use of Fenton Reaction in Drugs and Food

Molecules, Год журнала: 2022, Номер 27(17), С. 5451 - 5451

Опубликована: Авг. 25, 2022

Iron is the most abundant mineral in human body and plays essential roles sustaining life, such as transport of oxygen to systemic organs. The Fenton reaction between iron hydrogen peroxide, generating hydroxyl radical, which highly reactive toxic living cells. "Ferroptosis", a programmed cell death closely involved, has recently received much attention. Furthermore, various applications have been reported medical nutritional fields, cancer treatment or sterilization. Here, this review summarizes recent growing interest usefulness its biological relevance through basic practical information reports.

Язык: Английский

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Ultrahigh-Performance Fiber-Supported Iron-Based Ionic Liquid for Synthesizing 3,4-Dihydropyrimidin-2-(1H)-ones in a Cleaner Manner

Langmuir, Год журнала: 2024, Номер 40(18), С. 9579 - 9591

Опубликована: Апрель 24, 2024

Herein, a fiber-supported iron-based ionic liquid as type of fibrous catalyst has been developed for the synthesis bioactive 3,4-dihydropyrimidin-2-(1H)-ones (DHPMs) via three-component Biginelli reactions in cleaner manner. The described was obtained from commercially available polyetheretherketone (PEEK) fiber by postfunctionalization processes and characterized analyzed detail means diversified technologies. Furthermore, liquids could mediate classical to proceed smoothly gain variety substituted DHPMs with yields up 99%. superior catalytic activities were ascribed quasi-homogeneous medium generated surface layer PEEK fiber, which afford an appropriate reaction zone further be aggregation substrates facilitate reaction. Notably, is recycling over 10 runs just pair tweezers, operational procedure capable enlarging system gram-scale without any performance degradation, provided manner take advantage organic potential industrialization prospects.

Язык: Английский

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Merging Photoinduced Iron-Catalyzed Decarboxylation with Copper Catalysis for C–N and C–C Couplings

ACS Catalysis, Год журнала: 2023, Номер 13(3), С. 1678 - 1685

Опубликована: Янв. 13, 2023

We report a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. The ligand-to-iron charge transfer process under light was initially occurred to generate an unstabilized alkyl radical, and copper catalyst delivered enabled subsequent coupling reactions form C–N or C–C bonds. By merging iron-catalyzed with catalysis, this system allows smooth conversion wide range acids amination, decarboxylative dehydrogenation, alkylation efficiently. A variety complex drug natural molecules is applicable, suggesting that would facilitate rapid compound library synthesis benefit discovery pharmaceutical agents.

Язык: Английский

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Polyetheretherketone fiber-supported polyethylene glycols for phase-transfer catalysis in its surface layer

Colloids and Surfaces A Physicochemical and Engineering Aspects, Год журнала: 2024, Номер 694, С. 134160 - 134160

Опубликована: Май 3, 2024

Язык: Английский

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A Combined Spectroscopic and Computational Study on the Mechanism of Iron-Catalyzed Aminofunctionalization of Olefins Using Hydroxylamine Derived N–O Reagent as the “Amino” Source and “Oxidant”

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2637 - 2656

Опубликована: Фев. 4, 2022

Herein, we study the mechanism of iron-catalyzed direct synthesis unprotected aminoethers from olefins by a hydroxyl amine derived reagent using wide range analytical and spectroscopic techniques (Mössbauer, Electron Paramagnetic Resonance, Ultra-Violet Visible Spectroscopy, X-ray Absorption, Nuclear Resonance Vibrational resonance Raman) along with high-level quantum chemical calculations. The triflic acid salt acts as "oxidant" well "amino" group donor. It activates high-spin Fe(II) (St = 2) catalyst [Fe(acac)2(H2O)2] (1) to generate 5/2) intermediate (Int I), which decays second II) St 2. analysis computational data leads formulation Int I [Fe(III)(acac)2-N-acyloxy] (an alkyl-peroxo-Fe(III) analogue). Furthermore, II is formed N–O bond homolysis. However, it does not high-valent Fe(IV)(NH) species (a Fe(IV)(O) analogue), but instead Fe(III) center strongly antiferromagnetically coupled (J −524 cm–1) an iminyl radical, [Fe(III)(acac)2-NH·], giving Though Fe(NH) complexes isoelectronic surrogates Fe(O) functionalities are known, detection Fe(III)-N-acyloxy undergoes cleavage active iron–nitrogen II), unprecedented. Relative centers, features weak elongated Fe–N which, together unpaired electron density vector, helps rationalize its propensity for N-transfer reactions onto styrenyl olefins, resulting in overall formation aminoethers. This thus demonstrates potential utilizing iron-coordinated nitrogen-centered radicals powerful reactive intermediates catalysis.

Язык: Английский

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