Recent Advances in Constructing Nitrogen‐Containing Heterocycles <i>via</i> Electrochemical Dehydrogenation

Ye, Zenghui; Zhang, Fengzhi

doi:10.1002/cjoc.201900049

Cited by 67 publications

(20 citation statements)

References 104 publications

(3 reference statements)

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“…With the optimized reaction conditions defined, we set out to explore the scope of the electrooxidation of methylarenes. Notably, the site-selectivity was not significantly affected by introducing a phenyl (3), bromo (4), or cyano group (5) at C5, or by varying the substituent on N1 (6-9) or C2 (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29) of the C4,C6-dimethylated benzimidazole substrate (Fig. 2).…”

Section: Resultsmentioning

confidence: 99%

“…However, the installation of a carbamoyl group on N1 resulted in a slight decrease of regioselectivity (10). The method showed broad compatibility with common functional groups or moieties such as alkyl bromide (7), alkyne (8), alkene (9), ester (15,16), alcohol (17,18), ketone (19), aldehyde (20), Bocprotected amine (21)(22)(23), ketal (24), azido (25), and aromatic heterocycles (12, 13, 26, and 27). Molecular fragments derived from natural products dehydroabietic acid (28) and lithocholic acid (29) were equally well tolerated.…”

Section: Resultsmentioning

confidence: 99%

“…1a). As an alternative to chemical oxidation, electrooxidation eliminates the use of stoichiometric chemical oxidants and is attracting increasing interests [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] . Notably, electrooxidation of electron-rich toluene derivatives to substituted benzaldehydes has been applied in the industrial production of panisaldehyde and 3,4,5-trimethoxybenzaldehyde [27][28][29] .…”

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Site-selective electrooxidation of methylarenes to aromatic acetals

et al. 2020

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Aldehyde is one of most synthetically versatile functional groups and can participate in numerous chemical transformations. While a variety of simple aromatic aldehydes are commercially available, those with a more complex substitution pattern are often difficult to obtain. Benzylic oxygenation of methylarenes is a highly attractive method for aldehyde synthesis as the starting materials are easy to obtain and handle. However, regioselective oxidation of functionalized methylarenes, especially those that contain heterocyclic moieties, to aromatic aldehydes remains a significant challenge. Here we show an efficient electrochemical method that achieves site-selective electrooxidation of methyl benzoheterocycles to aromatic acetals without using chemical oxidants or transition-metal catalysts. The acetals can be converted to the corresponding aldehydes through hydrolysis in one-pot or in a separate step. The synthetic utility of our method is highlighted by its application to the efficient preparation of the antihypertensive drug telmisartan.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Site-selective electrooxidation of methylarenes to aromatic acetals

et al. 2020

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“…Recent years have witnessed dramatic increase in the use of radical‐based methods in synthetic applications due to the discovery of numerous friendly radical precursors and development of mild and selective methods for promoting radical reactions [3–5] . Organic electrochemistry is a well‐known tool for the generation of radical intermediates as molecules are converted to open shell species when they lose or take an electron on the electrode [6–15] . Electrochemical decarboxylation, which generates alkyl radicals, has been studied by Kolbe in the 1840s before the concept of radical is developed [16–17] .…”

Section: Introductionmentioning

confidence: 99%

Electrochemically Driven Radical Reactions: From Direct Electrolysis to Molecular Catalysis

Chen

2021

The Chemical Record

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Organic radicals are versatile synthetic intermediates that provide reactivities and selectivities complementary to ionic species. Despite its long history, electrochemically driven radical reactions remain limited in scope. In the past few years, there have been dramatic increase in research activity in organic electrochemistry. We have been developing electrochemical and electrophotocatalytic methods for the generation and synthetic utilization of organic radicals. In our studies, various radical species such as alkene and arene radical cations and carbon‐ and heteroatom‐centered radicals are generated from readily available precursors through direct electrolysis, molecular electrocatalysis or molecular electrophotocatalysis. These radical species undergo various inter‐ and intramolecular oxidative transformations to rapidly increase molecular complexity. The simultaneous occurrence of anodic oxidation and cathodic proton reduction allows the oxidative reactions to proceed through H2 evolution without external chemical oxidants.

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“…Organic electrochemistry, which drives redox processes with electric current, is increasingly considered as a highly sustainable and efficient synthetic method 21–34 . One key advantage of using electrochemical methods is that the reaction efficiency and selectivity can often be boosted by manipulating the electric current or potential, allowing one to achieve transformations that are otherwise synthetically inaccessible.…”

Section: Introductionmentioning

confidence: 99%

Practical and stereoselective electrocatalytic 1,2-diamination of alkenes

2019

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The 1,2-diamine motif is widely present in natural products, pharmaceutical compounds, and catalysts used in asymmetric synthesis. The simultaneous introduction of two amino groups across an alkene feedstock is an appealing yet challenging approach for the synthesis of 1,2-diamines, primarily due to the inhibitory effect of the diamine products to transition metal catalysts and the difficulty in controlling reaction diastereoselectivity and regioselectivity. Herein we report a scalable electrocatalytic 1,2-diamination reaction that can be used to convert stable, easily available aryl alkenes and sulfamides to 1,2-diamines with excellent diastereoselectivity. Monosubstituted sulfamides react in a regioselective manner to afford 1,2-diamines bearing different substituents on the two amino groups. The combination of an organic redox catalyst and electricity not only obviates the use of any transition metal catalyst and oxidizing reagent, but also ensures broad reaction compatibility with a variety of electronically and sterically diverse substrates.

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Recent Advances in Constructing Nitrogen‐Containing Heterocycles via Electrochemical Dehydrogenation

Abstract: In consideration of the importance of nitrogen‐containing heterocycles in both medicinal and material chemistry, herein, we intend to summarize the most recent advances about their synthesis by electrochemical dehydrogenation.

Cited by 67 publications

References 104 publications

Site-selective electrooxidation of methylarenes to aromatic acetals

Site-selective electrooxidation of methylarenes to aromatic acetals

Electrochemically Driven Radical Reactions: From Direct Electrolysis to Molecular Catalysis

Practical and stereoselective electrocatalytic 1,2-diamination of alkenes

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