Site-Selective Electrochemical C–H Silylations of Pyridines Enabled by Temporary Reductive Dearomatization
Site-selective pyridine C–H silylation chemistry is of significant value but remains underdeveloped. In this study, we demonstrated that electron-deficient pyridines are highly selectively reductively silylated at the C4-position under electrochemical reduction conditions. A diverse array of C4-silylated pyridines was synthesized in good-to-excellent yields using common chlorosilanes as activating agents. Additionally, the use of bulky chlorotriisopropylsilane led to the formation of the C5-silylated products, albeit in moderate yields. This method is noteworthy due to its mild reaction conditions, simplicity, and excellent site selectivity for a diverse range of pyridines. Mechanistic studies revealed that the reaction involves temporary dearomatization to yield a 1,4-disilylated compound, which is quickly converted into the final C4-silylated pyridine through hydrolysis and air-driven rearomatization..
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Preprint| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
chemRxiv.org - (2024) vom: 08. Apr. Zur Gesamtaufnahme - year:2024 |
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| Sprache: |
Englisch |
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| Beteiligte Personen: |
Yang, Zhihao [VerfasserIn] |
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| Links: |
Volltext [kostenfrei] |
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| doi: |
10.26434/chemrxiv-2024-bgpz1 |
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XCH043203906 |
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| 520 | |a Site-selective pyridine C–H silylation chemistry is of significant value but remains underdeveloped. In this study, we demonstrated that electron-deficient pyridines are highly selectively reductively silylated at the C4-position under electrochemical reduction conditions. A diverse array of C4-silylated pyridines was synthesized in good-to-excellent yields using common chlorosilanes as activating agents. Additionally, the use of bulky chlorotriisopropylsilane led to the formation of the C5-silylated products, albeit in moderate yields. This method is noteworthy due to its mild reaction conditions, simplicity, and excellent site selectivity for a diverse range of pyridines. Mechanistic studies revealed that the reaction involves temporary dearomatization to yield a 1,4-disilylated compound, which is quickly converted into the final C4-silylated pyridine through hydrolysis and air-driven rearomatization. | ||
| 650 | 4 | |a Chemistry |7 (dpeaa)DE-84 | |
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| 700 | 1 | |a Hao, Xin-Qi |e verfasserin |4 aut | |
| 700 | 1 | |a Song, Mao-Ping |e verfasserin |4 aut | |
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