Zhao Quan-Qing, Chen Jun, Zhou Xue-Song, Yu Xiao-Ye, Chen Jia-Rong, Xiao Wen-Jing
CCNU-uOttawa Joint Research Centre, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 345 Lingling Road, Shanghai, 200032, P. R. China.
Chemistry. 2019 Jun 18;25(34):8024-8029. doi: 10.1002/chem.201901665. Epub 2019 May 21.
Alkene bifunctionalizations are powerful tools for the rapid construction of structurally complex and valuable scaffolds, and such reactions typically involve the use of transition-metal catalysts or organocatalysts. Here, we report for the first time a photogenerated neutral nitrogen radical catalyzed intermolecular alkene bifunctionalization by using allyl sulfones as the source of both the carbon and the sulfone functionalities under mild conditions. The key to the success of this protocol involves the visible-light-mediated photocatalytic in situ generation of a nitrogen-centered radical from the N-(2-acetylphenyl) benzenesulfonamide catalyst, and its activation of the allyl sulfones to generate reactive species. The preliminary control experiments supported the postulated mechanism.
烯烃双官能团化反应是快速构建结构复杂且有价值的骨架的有力工具，此类反应通常涉及过渡金属催化剂或有机催化剂的使用。在此，我们首次报道了在温和条件下，以烯丙基砜作为碳官能团和砜官能团的来源，通过光生中性氮自由基催化的分子间烯烃双官能团化反应。该方法成功的关键在于可见光介导的光催化过程，即从N-(2-乙酰苯基)苯磺酰胺催化剂原位生成氮中心自由基，并使其激活烯丙基砜以产生活性物种。初步的对照实验支持了所提出的机理。
