Visible-light-induced coupling of carboxylic acids with alcohols/amines via a phosphorous linchpin strategy.
Visible-light-induced coupling of carboxylic acids with alcohols/amines via a phosphorous linchpin strategy.
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DOI：
10.1016/j.chempr.2023.04.011
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发表时间：
2023-05
期刊：
影响因子：
23.5
通讯作者：
Qiupeng Peng;A. R. Gogoi;Ángel Rentería-Gómez;O. Gutierrez;K. Scheidt
中科院分区：
文献类型：
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作者：
Qiupeng Peng;A. R. Gogoi;Ángel Rentería-Gómez;O. Gutierrez;K. Scheidt
将活化的羧酸和醇/胺组合以分别获得酯和酰胺是有机化学的基石，并且在过去的世纪中得到了很好的发展。由于这些官能团在生物活性分子中的普遍存在，这些脱水被广泛用于药物化学和天然产物合成。在这里，我们报告了一个与预期的酯/酰胺结果不同的过程，通过光诱导的活化羧酸和醇/胺的偶联，通过单电子化学有效地制备α-羟基/氨基酮或β-酮基膦酸酯。磷关键策略允许通过分子内三重态自由基过程组合这些简单试剂，从而能够形成新的碳-碳键。
The combination of activated carboxylic acids and alcohols/amines to access esters and amides, respectively, is a cornerstone of organic chemistry and has been well developed over the past century. These dehydrations are extensively used in medicinal chemistry and natural product synthesis due to the prevalence of these functional groups in bioactive molecules. Here, we report a divergent process from the expected ester/amide outcomes through a light-induced coupling of activated carboxylic acids and alcohols/amines to efficiently prepare α-hydroxy/amino ketones or β-ketophosphonates via single-electron chemistry. A phosphorous linchpin strategy allows for the combination of these simple reagents through an intramolecular triplet state radical process, thereby enabling new carbon–carbon bond formation.