Copper- or iron-catalyzed stereoselective methylation of enamides using dicumyl peroxide as the methyl source

Zhang, Fukuan; Liu, Haidong; Jia, Xin-Jian; Li, Lin; Liang, Yi; Luo, Xuzhong; Luo, Haiqing

doi:10.1039/d3nj02949b

Cited by 2 publications

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References 68 publications

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“…(Scheme 31g) 298 Recently, the Luo group discovered a method for the Fe-or Cu-catalyzed stereoselective radical C(sp 2 )−H methylation of enamides (31-50) using dicumyl peroxide as the methyl source (Scheme 31h). 299 After radicals are oxidized to cations by [Fe(III)] species, they can be attacked by various nucleophiles to achieve different C− H functionalization. In 2014, Bolm's group reported the Fecatalyzed C(sp 3 )−H sulfonylimidation of diarylmethanes (32-2) via an oxidative SET between diarylmethyl radicals and [Fe(III)] complexes (Scheme 32a).…”

Section: Radical Substitution Of Fe Complexesmentioning

confidence: 99%

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

Wang,

He,

Wang

et al. 2024

Chem. Rev.

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

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Section: Radical Substitution Of Fe Complexesmentioning

confidence: 99%

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

Wang,

He,

Wang

et al. 2024

Chem. Rev.

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“…In 2020, Punniyamurthy’s group developed a novel rhodium(III)-catalyzed tunable C4 alkylation and alkenylation of indoles with allyl alcohols by switching the additives or directing group (Scheme a), and this achievement was based on the use of aromatics as coupling partners with allyl alcohols. Considering the importance of alkenyl C(sp 2 )–H functionalization and our persistent attention on enamides, , this study attempts to describe rhodium-catalyzed switchable olefinic β-C(sp 2 )–H alkenylation and alkylation of acyclic enamides with allyl alcohols (Scheme b).…”

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confidence: 99%

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

Li,

Liu,

Song

et al. 2024

Org. Lett.

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Herein, rhodium(III)-catalyzed β-C(sp 2 )−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 of substrates and typically proceeded with excellent regioselectivity and stereoselectivity as well as with good functional group tolerance. The catalytic system offers an efficient approach for synthesizing various functionalized enamides bearing N-(2Z,4E)butadiene and (Z)-β-C(sp 2 )−H alkylated enamides. In addition, mechanistic experiments suggest that Rh(III)-catalyzed C−H activation is not related to the critical step.

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Copper- or iron-catalyzed stereoselective methylation of enamides using dicumyl peroxide as the methyl source

Abstract: An efficient and versatile copper- or iron-catalyzed direct β-C(sp2)-H methylation of enamides by using dicumyl peroxide (DCP) as the methylating reagent has been developed. This methodology provides a convenient access...

Cited by 2 publications

References 68 publications

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

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

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

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Copper- or iron-catalyzed stereoselective methylation of enamides using dicumyl peroxide as the methyl source

Abstract: An efficient and versatile copper- or iron-catalyzed direct β-C(sp2)-H methylation of enamides by using dicumyl peroxide (DCP) as the methylating reagent has been developed. This methodology provides a convenient access...

Cited by 2 publications

References 68 publications

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

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

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

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