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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Metal Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(2), P. 829 - 839

Published: Jan. 4, 2021

Density functional theory calculations were applied to study four previously published metal-catalyzed [2,3]-rearrangements from onium ylide intermediates, in pursuit of generalizations about when, during these types reactions, catalysts dissociate. Our results corroborate past studies where free-ylide mechanisms proposed be operative. Results on case indicate that the origin metal–catalyst dissociation can attributed primarily steric bulkiness groups adjacent carbene carbon.

Language: Английский

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A Recent Progress for the Synthesis of Thiocarboxylates

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(25)

Published: May 31, 2022

Abstract As a common and integral feature of many natural products, thiocarboxylates play an important role in biologically or pharmaceutically active compounds. Thiocarboxylates often show unique physiological activities biology drugs, which inspires new therapeutic drugs. The related research developments thioester‐based medicinal chemistry have been rapidly developing increasingly topic the last two decades. In this review, we will summarize main methods for synthesis thiocarboxylates, might provide general ideas to access more effective

Language: Английский

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Catalytic rearrangements of onium ylides in aromatic systems

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(17), P. 3427 - 3439

Published: Jan. 1, 2022

A review of recent advances in catalyst-controlled [2,3]- and [1,2]-rearrangements onium ylides aromatic systems.

Language: Английский

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Divergent Construction of α,α-Difunctionalized Ketones via [1,2]-Sigmatropic Rearrangement/Alkylation-Hydroxylation/Dialkylation of I^(III)/S^(VI) Ylides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

The rare [1,2]-sigmatropic rearrangement of sulfoxonium-iodonium hybrid ylides is described, which enables the efficient sulfoxidation/sulfonylation-alkylation I(III)/S(VI) with 1,3-dicarbonyls. By slight modification reaction conditions, controllable alkylation-hydroxylation and dialkylation were achieved. This strategy affords a diverse array α,α-difunctionalized ketones in moderate to good yields, demonstrating broad substrate scope. These findings provide an important advancement sulfoxonium highlight divergent reactivity ylides.

Language: Английский

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Silver-Catalyzed Doyle–Kirmse Reaction of Allyl Sulfides with Vinyl Triftosylhydrazones

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Here, we report a general and practical Doyle-Kirmse reaction of allyl/propargyl sulfides with donor-only vinyl carbenes generated in situ from triftosylhydrazones the presence silver catalyst. This protocol features mild conditions, exhibits broad substrate scope exceptional functional group tolerance, provides corresponding 1,5-dienyl 1,4-enallenyl high yields. Moreover, gram-scale synthesis, late-stage modifications complex molecules, post-synthetic transformations were performed to demonstrate applicability this protocol.

Language: Английский

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Doyle–Kirmse Reaction on Alkynyl Hydrazone Carboxylates: Synthesis of 1,4-Allenyne and 1,5-Enyne Thioaryl Carboxylates

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 2135 - 2140

Published: March 1, 2024

The first Doyle-Kirmse reaction on alkynyl diazoacetates using allyl/propargyl sulfides is reported. development provides diversified 1,5-enyne and 1,4-allenyne thioaryl carboxylates in good yields under ligand-/additive-free AuCl Rh

Language: Английский

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Gold‐catalyzed C−H Functionalization of Phenothiazines with Aryldiazoacetates

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(24), P. 5721 - 5727

Published: Oct. 15, 2020

Abstract Phenothiazine is an important structural motif in pharmaceuticals and advanced functional organic materials. However, the C−H functionalization reaction of N ‐protected phenothiazine rather unexplored often shadowed by its chemical reactivity on heteroatomic centers, which limits diversity potential applications. This report demonstrates a straightforward approach towards site‐selective at para ‐position atom via gold‐catalyzed carbene transfer reactions (37 examples, up to 83% yield). The mechanism behind regionselectivity was also elucidated combination computational experimental studies. magnified image

Language: Английский

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Doyle–Kirmse reaction using 3,3-difluoroallyl sulfide and N-sulfonyl-1,2,3-triazole: an efficient access to gem-difluoroallylated multifunctional quaternary carbon

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(32), P. 6974 - 6978

Published: Jan. 1, 2021

A Doyle-Kirmse reaction of N-sulfonyl-1,2,3-triazole with 3,3-difluoroallyl sulfide through a Rh(ii)-catalyzed [2,3]-sigmatropic rearrangement has been developed, which provides an efficient access to multifunctional quaternary centers containing aryl, imino, thio, and brominated gem-difluoroallyl groups. The features broad substrate scope moderate excellent yields. applicability the method is confirmed by gram-scale synthesis further transformations.

Language: Английский

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Borane-catalyzed arylation of aryldiazoacetates withN,N-dialkylanilines

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(20), P. 4101 - 4104

Published: Jan. 1, 2022

We report a catalytic Friedel–Crafts type arylation of donor–acceptor diazo compounds with aniline derivatives under metal-free and mild conditions.

Language: Английский

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