Practical Synthesis of Terminal Vinyl Fluorides.
Practical Synthesis of Terminal Vinyl Fluorides.
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DOI：
10.1021/acs.joc.3c00917
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发表时间：
2023-07
期刊：
影响因子：
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通讯作者：
I. Volchkov;Brent V. Powell;O. Zatolochnaya;Joyce C. Leung;S. Pennino;Lifen Wu;N. Gonnella;Bangaru Bhaskararao;M. Kozlowski;J. Reeves
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文献类型：
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作者：
I. Volchkov;Brent V. Powell;O. Zatolochnaya;Joyce C. Leung;S. Pennino;Lifen Wu;N. Gonnella;Bangaru Bhaskararao;M. Kozlowski;J. Reeves
高异构体纯度的二取代和三取代氟乙烯的合成一直是有机合成中的一个难题。虽然存在许多方法来获得这些化合物，但将所需异构体与次要异构体和/或起始材料分离通常是困难的。在此，我们报道了一种通过选择性Horner-Wadsworth-Emmons烯化/水解获得二-和三取代的氟乙烯的实用方法，其提供高（>98%）E-异构体纯度的结晶2-氟丙烯酸。随后的银催化立体保留脱羧提供了标题物质的异构体纯度高，而不需要繁琐的色谱法，以消除次要异构体。该方法适用于各种醛和酮，并提供了各种各样的二取代和三取代的氟乙烯。该序列被应用于合成抗菌和抗炎化合物。
The synthesis of di- and trisubstituted vinyl fluorides with high isomeric purity remains a challenge for organic synthesis. While many methods exist to access these compounds, the separation of the desired isomer from the minor isomer and/or starting materials often is difficult. Herein, we report a practical method to access di- and trisubstituted vinyl fluorides via a selective Horner-Wadsworth-Emmons olefination/hydrolysis, which provides crystalline 2-fluoroacrylic acids in high (>98%) E-isomeric purity. A subsequent silver-catalyzed stereoretentive decarboxylation provides the title substances with high isomeric purity and without the need for tedious chromatography to remove the minor isomer. The process was amenable to a variety of aldehydes and ketones and provided a diverse array of di- and trisubstituted vinyl fluorides. The sequence was applied to the synthesis of antibacterial and anti-inflammatory compounds.