Electrochemical radical–radical cross-coupling: direct access to β-amino nitriles from unactivated imines and alkyl nitriles

Zeng, Wei-Mei; Wang, Zhi-Lv; He, Yan‐Hong; Guan, Zhi

doi:10.1039/d2gc00457g

Cited by 15 publications

(3 citation statements)

References 51 publications

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“…As for the fate of III , it can be coupled with 2a to yield i-b (detected by HRMS) or further oxidized to form imine cation i-c , which can be attacked by CN – to produce i-d (detected by HRMS) , or hydrolyzed to amine and aldehyde. Imine 1 takes a proton from the system to become the protonated imine 1a , which is then converted to the α-amino radical I via a SET process of cathodic electrolysis . The protonated imine is more easily reduced than the neutral imine.…”

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confidence: 99%

Direct Reductive Arylation of Imines with Electron-Deficient (Hetero) Arenes via Electrosynthesis to Access Benzylic Amines

Zeng

Guan

2022

Org. Lett.

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In this paper, a direct access to benzylic amines from imines and electron-deficient (hetero) arenes via electrochemical radical−radical cross-coupling is described. The reaction has the characteristics of the wide range of substrates, excellent functional group tolerance, metal-free and highly atom-economical. The insensitivity to air and moisture makes this synthetic strategy more efficient for the construction of various benzylic amine derivatives.

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confidence: 99%

Direct Reductive Arylation of Imines with Electron-Deficient (Hetero) Arenes via Electrosynthesis to Access Benzylic Amines

Zeng

Guan

2022

Org. Lett.

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“…4 A . Initially, TEMP undergoes hydroxylation, generating the EPR-silent TEMPO–H ( 37 ), which is then further oxidized by PMS to TEMPO–OH ( 38 ). TEMPO–OH can react with TEMPO–H, forming two molecules of TEMPO ( Pathway 1 ).…”

Section: Resultsmentioning

confidence: 99%

Unveiling singlet oxygen spin trapping in catalytic oxidation processes using in situ kinetic EPR analysis

Chen

Yang

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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Singlet oxygen ( 1 O 2 ) plays a pivotal role in numerous catalytic oxidation processes utilized in water purification and chemical synthesis. The spin-trapping method based on electron paramagnetic resonance (EPR) analysis is commonly employed for 1 O 2 detection. However, it is often limited to time-independent acquisition. Recent studies have raised questions about the reliability of the 1 O 2 trapper, 2,2,6,6-tetramethylpiperidine (TEMP), in various systems. In this study, we introduce a comprehensive, kinetic examination to monitor the spin-trapping process in EPR analysis. The EPR intensity of the trapping product was used as a quantitative measurement to evaluate the concentration of 1 O 2 in aqueous systems. This in situ kinetic study was successfully applied to a classical photocatalytic system with exceptional accuracy. Furthermore, we demonstrated the feasibility of our approach in more intricate 1 O 2 -driven catalytic oxidation processes for water decontamination and elucidated the molecular mechanism of direct TEMP oxidation. This method can avoid the false-positive results associated with the conventional 2D 1 O 2 detection techniques, and provide insights into the reaction mechanisms in 1 O 2 -dominated catalytic oxidation processes. This work underscores the necessity of kinetic studies for spin-trapping EPR analysis, presenting an avenue for a comprehensive exploration of the mechanisms governing catalytic oxidation processes.

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“…for their activation, which limits their reaction scope and functional compatibility (Scheme a) . Thus, the development of a superior cyanoalkylation of imines is highly desired, especially under metal-free and oxidant-free conditions; however, it is rarely reported …”

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confidence: 99%

Direct Cyanoalkylation of Imines Driven by a Photoactive Electron Donor–Acceptor Complex

Liu,

Hou,

Jing

et al. 2024

Org. Lett.

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β-Amino nitriles are important molecular scaffolds. Cyanoalkylation of imines is the most straightforward method for the construction of these scaffolds. In this study, we report the novel cyanoalkylation of imines via radical coupling enabled by a photoactive electron donor−acceptor complex. This strategy is characterized by mild conditions, broad reaction scopes, and high atom economy. The scalability and practicality of this strategy are demonstrated by a 40 g continuous flow system from which a variety of important pharmaceutical-related molecules were obtained.

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Electrochemical radical–radical cross-coupling: direct access to β-amino nitriles from unactivated imines and alkyl nitriles

Abstract: In this article, a direct access to β-amino nitriles from unactivated imines and alkyl nitriles by electrochemical radical-radical cross-coupling was described for the first time. The use of abundant and...

Cited by 15 publications

References 51 publications

Direct Reductive Arylation of Imines with Electron-Deficient (Hetero) Arenes via Electrosynthesis to Access Benzylic Amines

Direct Reductive Arylation of Imines with Electron-Deficient (Hetero) Arenes via Electrosynthesis to Access Benzylic Amines

Unveiling singlet oxygen spin trapping in catalytic oxidation processes using in situ kinetic EPR analysis

Direct Cyanoalkylation of Imines Driven by a Photoactive Electron Donor–Acceptor Complex

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