Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

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Rhodium(III)-Catalyzed Switchable β-C(sp²)–H Alkenylation and Alkylation of Acyclic Enamides with Allyl Alcohols

Organic Letters, Journal Year: 2024, Volume and Issue: 26(17), P. 3673 - 3678

Published: April 19, 2024

Herein, rhodium(III)-catalyzed β-C(sp2)–H alkenylation and alkylation of enamides are presented using readily accessible allylic alcohols by switching the reaction conditions. This tunable transformation has been applied to a wide range substrates typically proceeded with excellent regioselectivity stereoselectivity as well good functional group tolerance. The catalytic system offers an efficient approach for synthesizing various functionalized bearing N-(2Z,4E)-butadiene (Z)-β-C(sp2)–H alkylated enamides. In addition, mechanistic experiments suggest that Rh(III)-catalyzed C–H activation is not related critical step.

Language: Английский

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Three‐Component 1,2‐Methylamidation of Alkynes via Coordinating Activation Strategy

ChemistryOpen, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

The selective functionalization of carbon–carbon triple bonds with methyl groups remains a challenging task. Herein, the successful development novel copper‐catalyzed three‐component 1,2‐methylamidation bond is reported. readily available coupling partners, picolinamides and alkynes dicumyl peroxide, serve as both source oxidant in this difunctional strategy to access methylated enamides; substrate scope broad, demonstrating good functional group compatibility. synthetic utility reaction also demonstrated through via late‐stage substrates bearing biologically relevant molecules.

Language: Английский

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Magic methylation with methyl-containing peroxides

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

Published: Dec. 4, 2024

Methyl groups are abundant in pharmaceuticals, and their installation has garnered significant attention. This review summarises advancements the use of methyl-containing peroxides as reagents for a variety methylation reactions.

Language: Английский

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