Visible‐Light‐Enabled Trifluoromethylative Pyridylation of Alkenes from Pyridines and Triflic Anhydride

Lee, Kangjae; Lee, Seojin; Kim, Nam Hoon; Kim, Seonyul; Hong, Sungwoo

doi:10.1002/ange.202004439

Cited by 23 publications

(2 citation statements)

References 96 publications

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“…As pyridine surrogates, N-substituted pyridinium salts have bolstered the development of numerous visible-light induced reactions where radicals are produced via photocatalysts or electron donor-acceptor (EDA) complex formations. These radicals initiate a hydrogen atom transfer (HAT) or react with unsaturated carbon species, giving rise to complex radical species that can be sequestered in the pyridinium salts (Kim et al, 2019;Lee et al, 2020;Mathi et al, 2020). Of particular interest is the site-selective functionalization controlled by the N-substituents attached to the pyridinium salts (Jung et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

Nucleophilic C4-selective (hetero) arylation of pyridines for facile synthesis of heterobiaryls

Kim,

You,

Hong

2023

Front. Chem.

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The synthesis of heterobiaryl compounds holds significant value in organic chemistry due to their extensive range of applications. Herein, we report a highly efficient strategy for conducting C4-selective (hetero) arylation of pyridines using N-aminopyridinium salts. The reaction proceeds readily at room temperature in the presence of a base, thus eliminating the requirement for catalysts or oxidants. This method allows for the installation of various electron-rich (hetero) aryl groups on pyridines, resulting in the streamlined synthesis of highly valuable C4-(hetero) aryl pyridine derivatives, which are otherwise challenging to acquire via conventional methods. This simple and straightforward method will facilitate access to a range of heterobiaryl compounds thereby promoting their application in various scientific disciplines.

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Section: Introductionmentioning

confidence: 99%

Nucleophilic C4-selective (hetero) arylation of pyridines for facile synthesis of heterobiaryls

Kim,

You,

Hong

2023

Front. Chem.

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“…[1] Over the past few decades, radical-mediated alkene difunctionalizations offers a robust toolkit to obtain numerous high value-added products. [2] This process facilitates the incorporation of an alkenyl or alkynyl into target compounds, giving rise to multi-functionalized alkene or alkyne adducts. The general protocol is initiated by the addition of an external radical to an alkene, form-ing a new alkyl radical intermediate which is involved in the ensuing transition-metal catalyzed cross-couplings, [2d,e,k,n,o] or trapped by radical acceptors, [2g, 3] such as the Fuchs reagent (Scheme 1 A, a).…”

mentioning

confidence: 99%

Alkene Difunctionalization Triggered by a Stabilized Allenyl Radical: Concomitant Installation of Two Unsaturated C−C Bonds

Wei

Zhang

et al. 2021

Angewandte Chemie

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Radical-mediated difunctionalization of alkenes provides a promising approach to introduce one alkenyl or alkynyl group to target compounds. However, simultaneous installation of two unsaturated C À C bonds via alkene difunctionalization remains elusive, attributable to the high instability and transient lifetimes of alkenyl and alkynyl radicals. Herein, we report the photocatalytic 1,2-alkynylalkenylation and 1,2enynylalkenylation of alkenes for the first time, triggered by the intermolecular addition of a stabilized allenyl radical to an alkene. A portfolio of strategically designed, easily accessible dual-function reagents are applied to a radical dockingmigration cascade. The protocol has broad substrate scope and efficiently increases the degree of unsaturation.Scheme 1. Incorporation of unsaturated CÀC bonds via radical-mediated alkene difunctionalization.

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Photocatalytic Vicinal Aminopyridylation of Methyl Ketones by a Double Umpolung Strategy

Choi

Hong

2020

Angewandte Chemie

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A photocatalytic double umpolung strategy for the vicinal aminopyridylation of ketones was developed using pyridinium N−N ylides. The inversion of the polarity of the pyridinium N−N ylides by single‐electron oxidation successfully enables radical‐mediated 1,3‐dipolar cycloadditions with enolsilanes formed in situ from ketones, followed by homolytic cleavage of the N−N bond. Intriguingly, the nucleophilic amino and electrophilic pyridyl groups in the ylides can be installed at the nucleophilic α‐position and electrophilic carbonyl carbon, respectively, which are typically inaccessible by their innate polarity‐driven reactivity. This method accommodates a broad scope, and the utility was further demonstrated by the late‐stage functionalization of complex biorelevant molecules. Moreover, the strategy can be successfully applied to enamides.

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Visible‐Light‐Enabled Trifluoromethylative Pyridylation of Alkenes from Pyridines and Triflic Anhydride

Cited by 23 publications

References 96 publications

Nucleophilic C4-selective (hetero) arylation of pyridines for facile synthesis of heterobiaryls

Nucleophilic C4-selective (hetero) arylation of pyridines for facile synthesis of heterobiaryls

Alkene Difunctionalization Triggered by a Stabilized Allenyl Radical: Concomitant Installation of Two Unsaturated C−C Bonds

Photocatalytic Vicinal Aminopyridylation of Methyl Ketones by a Double Umpolung Strategy

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