德国亚琛工业大学Leonori, Daniele团队报道了光激发硝基芳烃用于烯烃氧化裂解。相关研究成果发表在2022年8月23日出版的《自然》。

烯烃的氧化裂解是将原料转化为高价值合成中间体的一个整体过程。在一个化学步骤中实现这一点的最可行方法是使用臭氧，然而，由于臭氧分解产物的爆炸性，会带来技术和安全挑战。

该文中，研究人员公开了一种使用硝基芳烃和紫光照射实现烯烃氧化裂解的替代方法。研究证明，光激发硝基芳烃是有效的臭氧替代物，与烯烃进行简单的自由基[3+2]环加成。生成的“N-掺杂”臭氧层在温和水解条件下可安全处理并生成相应的羰基产物。这些特征使得能够在广泛使用的有机官能团存在下控制所有类型的烯烃的裂解。此外，通过利用电子、空间和介导的极性效应，硝基芳烃的结构和功能多样性提供了一个模块化平台，以在含有一种以上烯烃的底物中获得位点选择性。

附：英文原文

Title: Photoexcited Nitroarenes for the Oxidative Cleavage of Alkenes

Author: Ruffoni, Alessandro, Hampton, Charlotte, Simonetti, Marco, Leonori, Daniele

Issue&Volume: 2022-08-23

Abstract: The oxidative cleavage of alkenes is an integral process that converts feedstock materials into high-value synthetic intermediates1,2,3. The most viable method to achieve this in one chemical step is with ozone4,5,6,7, which however poses technical and safety challenges owing to the explosive nature of ozonolysis products8,9. Herein, we disclose an alternative approach to achieve oxidative cleavage of alkenes using nitroarenes and purple light irradiation. We demonstrate that photoexcited nitroarenes are effective ozone surrogates that undergo facile radical [3+2] cycloaddition with alkenes. The resulting “N-doped” ozonides are safe to handle and lead to the corresponding carbonyl products under mild hydrolytic conditions. These features have enabled the controlled cleavage of all types of alkenes in the presence of a broad array of commonly used organic functionalities. Furthermore, by harnessing electronic, steric, and mediated polar effects, the structural and functional diversity of nitroarenes has provided a modular platform to obtain site-selectivity in substrates containing more than one alkene.

DOI: 10.1038/s41586-022-05211-0

Source: https://www.nature.com/articles/s41586-022-05211-0