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

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2759 - 2852

Published: Jan. 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

Language: Английский

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Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

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Recent progress in the application of iodonium ylides in organic synthesis

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(24), P. 6999 - 7015

Published: Jan. 1, 2022

This review summarizes the recent advances in synthetic application of iodonium ylides covering 2017 to 2022.

Language: Английский

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Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4422 - 4428

Published: June 8, 2023

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions N-nitrosoanilines with iodonium ylides. Mechanistically, formation former involves an unprecedented process including nitroso group-directed C(sp2)–H bond alkylation N-nitrosoaniline ylide followed by intramolecular C-nucleophilic addition to moiety, solvent-assisted cyclohexanedione ring opening, and transesterification/annulation. On contrary, latter initial annulation denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, clean sustainable oxidant (air), valuable products that are structurally diverse. In addition, utility was showcased their facile diverse transformations into synthetically biologically interesting compounds.

Language: Английский

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Accessing 7,8-Dihydroquinoline-2,5-diones via Rh-Catalyzed Olefinic C–H Activation/[4+2] Cyclization

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5136 - 5140

Published: June 7, 2024

Herein, we report a rhodium-catalyzed C–H activation/[4+2] cyclization reaction between α,β-unsaturated amides and iodonium ylides for the synthesis of novel 7,8-dihydroquinoline-2,5-diones analogues. This protocol provides series pyridones fused with saturated cycles good functional group compatibility, water air tolerance, to excellent yields under mild green conditions. Additionally, scale-up can be smoothly performed as low 0.25 mol % catalyst loading. Recycling experiments different transformation were also carried out demonstrate potential synthetic utility this protocol.

Language: Английский

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Rh(iii)-Catalyzed C(sp²)–H functionalization/cyclization cascade of N-carboxamide indole and iodonium reagents for access to indoloquinazolinone derivatives

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(17), P. 6337 - 6340

Published: Jan. 1, 2021

The sustainable synthesis of indoloquinazolinone derivatives from N -methoxycarbamoyl indoles and iodonium ylide reagents in methanol is described.

Language: Английский

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Divergent synthesis of fused N-heterocyclesviarhodium-catalysed [4 + 2] cyclization of pyrazolidinones with iodonium ylides

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2181 - 2186

Published: Jan. 1, 2022

We developed a catalytic system-controlled tunable strategy for the divergent synthesis of cinnolines and pyrazolo[1,2- ]cinnolines via rhodium-catalyzed [4 + 2] cyclization easily available pyrazolidinones iodonium ylides.

Language: Английский

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The solvent-controlled Rh(iii)-catalyzed switchable [4+2] annulation of 2-arylIndoles with iodonium ylides

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(41), P. 6140 - 6143

Published: Jan. 1, 2022

Highly selective and switchable [4+2] annulations of 2-arylindoles with iodonium ylides were achieved by performing solvent-controlled Rh(III)-catalyzed C-H activations. When using DCM as a solvent, the functionalization selectively delivered indolo[2,1-a]isoquinoline derivatives. In contrast, same catalytic system polar HFIP solvent predominately provided benzo[a]carbazole moieties.

Language: Английский

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Rh(iii)-catalyzed C–H annulation of sulfoxonium ylides with iodonium ylides towards isocoumarins

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(5), P. 1112 - 1116

Published: Jan. 1, 2022

The direct synthesis of isocoumarin skeletons has been realized through the Rh( iii )-catalyzed [3 + 3] annulation sulfoxonium ylides and iodonium under mild conditions.

Language: Английский

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Ru(II)-Catalyzed Decarbonylative Alkylation and Annulations of Benzaldehydes with Iodonium Ylides under Chelation Assistance

Organic Letters, Journal Year: 2022, Volume and Issue: 24(29), P. 5281 - 5286

Published: July 18, 2022

A Ru(II)-catalyzed decarbonylative alkylation and annulation of salicylaldehydes 2-aminobenzaldehydes with iodonium ylides has been developed for the synthesis dibenzo[b,d]furans NH-free carbazolones. The reaction proceeds smoothly under mild conditions a low catalyst loading broad substrate compatibility. Notably, hydroxy free amino groups were demonstrated to be effective directing groups, enabling successful aldehyde C–H bond activation subsequent decarbonylation inexpensive Ru(II) catalyst.

Language: Английский

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