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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Iron(III)-based metalloradical catalysis for asymmetric cyclopropanation via a stepwise radical mechanism

Nature Chemistry, Год журнала: 2023, Номер 15(11), С. 1569 - 1580

Опубликована: Сен. 7, 2023

Язык: Английский

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The chemistry of heterocycles in the 21st century

Russian Chemical Reviews, Год журнала: 2024, Номер 93(7), С. RCR5125 - RCR5125

Опубликована: Июль 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.

Язык: Английский

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Photocatalytic gem‐Difluoroolefination Reactions by a Formal C−C Coupling/Defluorination Reaction with Diazoacetates

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(4)

Опубликована: Окт. 30, 2021

The photolysis of diazoalkanes to conduct singlet carbene transfer reactions colored has recently attracted significant interest in organic synthesis. Herein, we describe a photocatalytic approach that allows the access triplet intermediates via energy highly efficient gem-difluoroolefination with α-trifluoromethyl styrenes. use tertiary amines proved pivotal unlock this unusual reaction pathway and prevent undesired cyclopropanation pathways. amine further facilitates ultimate abstraction fluoride yield gem-difluoroolefins (43 examples, up 88 % yield), which is supported by experimental theoretical mechanistic studies. We explored synthesis method broad substrate scope, ranging from simple olefins heterocyclic towards decoration pharmaceutically relevant building blocks.

Язык: Английский

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Visible-Light-Mediated Formal Carbene Insertion Reaction: Enantioselective Synthesis of 1,4-Dicarbonyl Compounds Containing All-Carbon Quaternary Stereocenter

ACS Catalysis, Год журнала: 2022, Номер 12(9), С. 5510 - 5516

Опубликована: Апрель 25, 2022

We developed an efficient visible-light-mediated formal carbene insertion reaction of 1,3-diketones with diazoesters for the construction enantioenriched 1,4-dicarbonyl compounds a quaternary carbon center. Combining visible light and Brønsted acid catalyst, chiral were achieved in good yields high enantioselectivities by photochemical transfer protocol.

Язык: Английский

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Tunable Key [3 + 2] and [2 + 1] Cycloaddition of Enaminones and α-Diazo Compounds for the Synthesis of Isomeric Isoxazoles: Metal-Controlled Selectivity

Organic Letters, Год журнала: 2023, Номер 25(12), С. 2139 - 2144

Опубликована: Март 22, 2023

The three-component reactions of enaminones, α-diazo esters/ketones, and t-butyl nitrite (TBN) for the switchable synthesis isomeric isoxazoles have been realized. catalysis with Cu(II) salt provides 3,4-disubsituted via [3 + 2] cycloaddition. On other hand, Ag(I) identical substrates leads to reversed C3 C4 substitution based on a key [2 1]

Язык: Английский

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Cobalt(II)–tetraphenylporphyrin-catalysed carbene transfer from acceptor–acceptor iodonium ylides via N-enolate–carbene radicals

Nature Chemistry, Год журнала: 2022, Номер 14(5), С. 550 - 557

Опубликована: Март 24, 2022

Язык: Английский

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Carbene Radicals in Transition-Metal-Catalyzed Reactions

ACS Catalysis, Год журнала: 2023, Номер 13(8), С. 5428 - 5448

Опубликована: Апрель 6, 2023

Discovered as organometallic curiosities in the 1970s, carbene radicals have become a staple modern-day homogeneous catalysis. Carbene exhibit nucleophilic radical-type reactivity orthogonal to classical electrophilic diamagnetic Fischer carbenes. Their successful catalytic application has led synthesis of myriad carbo- and heterocycles, ranging from simple cyclopropanes more challenging eight-membered rings. The field matured employ densely functionalized chiral porphyrin-based platforms that high enantio-, regio-, stereoselectivity. Thus far focus largely been on cobalt-based systems, but interest growing for past few years expand other transition metals. This Perspective covers advances made since 2011 gives an overview coordination chemistry, reactivity, radical species using metal complexes catalysts.

Язык: Английский

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Complete integration of carbene-transfer chemistry into biosynthesis

Nature, Год журнала: 2023, Номер 617(7960), С. 403 - 408

Опубликована: Май 3, 2023

Язык: Английский

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Synthesis and Characterization of Donor–Acceptor Iron Porphyrin Carbenes and Their Reactivities in N–H Insertion and Related Three-Component Reaction

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(9), С. 4934 - 4939

Опубликована: Фев. 22, 2023

Iron porphyrin carbenes (IPCs) have been extensively recognized as the reactive intermediates in various iron porphyrin-catalyzed carbene transfer reactions. While donor–acceptor diazo compounds frequently used for such transformations, structures and reactivities of IPCs are less explored. To date, no crystal IPC complexes reported, therefore, involvement intermediacy transformations lacks direct evidence. Here we report synthesis NMR characterization several from corresponding compounds. The X-ray structure an complex derived a morpholine-substituted amide was obtained. those were tested by N–H insertion reactions with aniline or morpholine well three-component reaction γ,δ-unsaturated α-keto ester based on electrophilic trapping ammonium ylide intermediate. Based these results, identified real

Язык: Английский

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