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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Application of sulfoxonium ylide in transition-metal-catalyzed C-H bond activation and functionalization reactions

Tetrahedron, Journal Year: 2021, Volume and Issue: 101, P. 132478 - 132478

Published: Oct. 8, 2021

Language: Английский

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Rh(III)-Catalyzed Chemodivergent Annulations between Indoles and Iodonium Carbenes: A Rapid Access to Tricyclic and Tetracyclic N-Heterocylces

Organic Letters, Journal Year: 2021, Volume and Issue: 23(11), P. 4233 - 4238

Published: May 21, 2021

Herein, we report an acid-controlled highly tunable selectivity of Rh(III)-catalyzed [4 + 2] and [3 3] annulations N-carboxamide indoles with iodonium ylides lead to form synthetically important tricyclic tetracyclic N-heterocycles. Here, ylide serves as a carbene precursor. The protocol proceeds under operationally simple conditions provides novel scaffolds such 3,4-dihydroindolo[1,2-c]quinazoline-1,6(2H,5H)-dione 1H-[1,3]oxazino[3,4-a]indol-1-one derivatives broad range functional group tolerance moderate excellent yields. Furthermore, the synthetic utility was extended for various chemical transformations easily scaled up large-scale level.

Language: Английский

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Recent advances in the reactions of silacyclobutanes and their applications

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(10), P. 2840 - 2855

Published: Jan. 1, 2022

This review summarizes the growing landscape in reactions of silacyclobutanes (SCBs) by highlighting fascinating progress, deconstructing mechanistic underpinnings, and drawing insight from related ring-opening expanding SCBs.

Language: Английский

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Transition‐Metal‐Catalyzed C−H Bond Functionalization of Arenes/Heteroarenes via Tandem C−H Activation and Subsequent Carbene Migratory Insertion Strategy

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 4088 - 4122

Published: Oct. 14, 2021

Abstract The past decade has witnessed tremendous developments in transition‐metal‐catalyzed C−H bond activation and subsequent carbene migratory insertion reactions, thus assisting the construction of diverse arene/heteroarene scaffolds. Various transition‐metal catalysts serve this purpose provide efficient pathways for an easy access to substituted heterocycles. A brief introduction metal‐carbenes been provided along with key mechanistic underlying coupling reactions. review is a concise knowledge about directing group‐assisted varied arenes/heteroarenes acceptor‐acceptor/donor‐acceptor diazo compounds. also highlights synthesis various carbocycles fused heterocycles through pathways, via C−C, C−N C−O forming mechanism usually involves process, followed by leading coupling.

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 Dual C–H Activation/Cascade Annulation of Benzimidates and CF₃-Imidoyl Sulfoxonium Ylides for the Synthesis of Trifluoromethyl-Decorated Benzo[de][1,8]naphthyridines

Organic Letters, Journal Year: 2022, Volume and Issue: 24(48), P. 8864 - 8869

Published: Dec. 1, 2022

An efficient and straightforward approach for the synthesis of trifluoromethyl-decorated benzo[de][1,8]naphthyridines has been achieved via Rh(III)-catalyzed dual C-H activation cascade annulation benzimidates CF3-imidoyl sulfoxonium ylides. The novel transformation involves formation four new chemical bonds along with release two molecules dimethyl sulfoxide (DMSO) one molecule each ethanol amine. optoelectronic properties obtained fused aromatic products have investigated by recording UV-vis absorption emission spectra.

Language: Английский

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Synthesis of α-Carbonyl-α′-amide Sulfoxonium Ylides from Isocyanates with Complete Atom Economy

Organic Letters, Journal Year: 2023, Volume and Issue: 25(7), P. 1214 - 1217

Published: Feb. 9, 2023

An efficient catalyst- and additive-free facile synthesis of α-carbonyl-α′-amide sulfoxonium ylides from isocyanates β-ketosulfoxonium with complete atom economy has been described. The adorned various functional groups were well-tolerated afforded moderate to high yields the ylide derivatives. Finally, using large-scale reactions converting synthesized into other valuable compounds, we demonstrated practicality this synthetic method.

Language: Английский

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Iodonium ylides: an emerging and alternative carbene precursor for C–H functionalizations

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(1), P. 24 - 38

Published: Nov. 23, 2022

The metal-catalyzed successive activation and functionalization of arene/heteroarene is one the most fundamental transformations in organic synthesis leads to privileged scaffolds natural products, pharmaceuticals, agrochemicals, fine chemicals. Particularly, transition-metal-catalyzed C-H arenes with carbene precursors via metal migratory insertion has been well studied. As a result, diverse have evaluated, such as diazo compounds, sulfoxonium ylides, triazoles, etc. In addition, there significant developments use iodonium ylides recent years, these reactions proceed high efficiencies selectivities. This review provides comprehensive overview functionalizations, including scope, limitations, their potential synthetic applications.

Language: Английский

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