Zhang Haoyu, Guan Shiyong, Chen Hanbo, Zhang Genhong, Chen Yuegang
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China.
Zhejiang Sci-Tech University Shengzhou Innovation Research Institute, Shengzhou 312400, China.
JACS Au. 2025 Apr 11;5(4):1932-1939. doi: 10.1021/jacsau.5c00154. eCollection 2025 Apr 28.
This work presents a feasible method for the elimination of alcohol hydroxyls through the direct activation of typical alkyl alcohols using neutral boron radicals. This transformation necessitates a proficient reagent capable of swiftly activating the alcohol hydroxyl group to produce radicals, thereby circumventing numerous alternative side reactions associated with the alcohol hydroxyl group. To implement this method, we have created an innovative photocatalytic reaction system that oxidizes sodium tetraphenylboron to produce neutral boron radicals, which subsequently enable the direct homolytic conversion of alcohol hydroxyl groups. This deoxygenation technique necessitates no additional preactivation of the alcohol and yields favorable outcomes for the majority of alcohol substrates. The technique facilitates the direct methylene reduction of aldehydes and ketones. Mechanistic studies have established that the reaction likely initiates with the production of alcohols, thereafter undergoing dehydroxylation to yield methylene-reduced products.
这项工作提出了一种通过使用中性硼自由基直接活化典型烷基醇来消除醇羟基的可行方法。这种转化需要一种能够迅速活化醇羟基以产生自由基的高效试剂，从而避免与醇羟基相关的许多其他副反应。为了实施该方法，我们创建了一种创新的光催化反应体系，该体系将四苯基硼酸钠氧化以产生中性硼自由基，随后这些自由基能够实现醇羟基的直接均裂转化。这种脱氧技术无需对醇进行额外的预活化，并且对大多数醇底物都能产生良好的效果。该技术有助于醛和酮的直接亚甲基还原。机理研究表明，反应可能始于醇的生成，随后进行脱羟基反应以生成亚甲基还原产物。
