Theoretical studies on Mn-catalyzed intermolecular allylic C-H aminations of internal olefins: mechanism, chemo- and regioselectivity

Wang, Juping; Xiao, Rongxing; Zheng, Kang‐Cheng; Li, Qian

doi:10.1016/j.mcat.2022.112278

Cited by 3 publications

(2 citation statements)

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“…Our group has engaged in theoretical investigations on the mechanisms of C-N bond formation by means of C-H amination based on metal or metalloenzyme catalysis. [32][33][34][35][36][37] Herein, a detailed mechanism of [Ni]H-catalyzed C(sp 3 )-H hydroamidation was investigated and the origin of insertion selectivity was explored with the aid of DFT calculations. These insights provide valuable information for constructing and developing highly efficient and selective remote C(sp 3 )-H hydroamidation systems.…”

Section: Textmentioning

confidence: 99%

Computational insights into the [Ni]H-catalyzed remote C(sp³)–H hydroamidation of alkenes: mechanism and insertion selectivity

Wang

Zheng

Lin

et al. 2022

Catal. Sci. Technol.

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Section: Textmentioning

confidence: 99%

Computational insights into the [Ni]H-catalyzed remote C(sp³)–H hydroamidation of alkenes: mechanism and insertion selectivity

Wang

Zheng

Lin

et al. 2022

Catal. Sci. Technol.

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“…In addition, these experiments also successfully constructed quaternary amino carbonyls that were hard to be realized by previous reports. , Although these Ir-catalyzed α-amidation reactions have obvious advantages such as high yield, excellent selectivity, and broad substrate scope, the mechanism and the origin of selectivity remain to be unraveled up to now. Our groups have been devoted to theoretical studies on nitrene transfer reactions. − Herein, density functional theory (DFT) calculations were carried out to explore the mechanism, reactivity, and determinants of the selectivity for the Ir-catalyzed intermolecular α-amidation of 2-acylimidazoles.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Ir-Catalyzed α-Amidation of 2-Acylimidazoles: Mechanism and Insertion Selectivity

et al. 2022

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The mechanism and reactivity of Ir-catalyzed α-amidation of 2-acylimidazoles have been investigated at the B3LYP-D3 level, with the emphasis on nitrene insertion selectivity. The calculation results show that the catalytic mechanism consists of iridacycle formation, CO2 release, nitrene insertion, and amido protonation processes. Thereinto, nitrene insertion is both rate- and selectivity-determining steps. The origin of the nitrene group favorably inserting into an Ir–Cα over Cγ–H bond was further unraveled. In addition, this work also explored the α-amidation reactivity difference between α-mono- and α,α-di-substituted 2-acylimidazoles and the source of this difference was identified. These meaningful insights may serve as the basis for the further design and development of transition-metal-catalyzed α-amidation systems featuring high reactivity and selectivity.

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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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Theoretical studies on Mn-catalyzed intermolecular allylic C-H aminations of internal olefins: mechanism, chemo- and regioselectivity

Cited by 3 publications

References 48 publications

Computational insights into the [Ni]H-catalyzed remote C(sp³)–H hydroamidation of alkenes: mechanism and insertion selectivity

Computational insights into the [Ni]H-catalyzed remote C(sp³)–H hydroamidation of alkenes: mechanism and insertion selectivity

Theoretical Study on Ir-Catalyzed α-Amidation of 2-Acylimidazoles: Mechanism and Insertion Selectivity

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

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Theoretical studies on Mn-catalyzed intermolecular allylic C-H aminations of internal olefins: mechanism, chemo- and regioselectivity

Cited by 3 publications

References 48 publications

Computational insights into the [Ni]H-catalyzed remote C(sp3)–H hydroamidation of alkenes: mechanism and insertion selectivity

Computational insights into the [Ni]H-catalyzed remote C(sp3)–H hydroamidation of alkenes: mechanism and insertion selectivity

Theoretical Study on Ir-Catalyzed α-Amidation of 2-Acylimidazoles: Mechanism and Insertion Selectivity

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

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Computational insights into the [Ni]H-catalyzed remote C(sp³)–H hydroamidation of alkenes: mechanism and insertion selectivity

Computational insights into the [Ni]H-catalyzed remote C(sp³)–H hydroamidation of alkenes: mechanism and insertion selectivity