钌催化未活化丙二烯与炔烃的分子间[2+2]环加成反应及其异常区域选择性
Ruthenium-Catalyzed Intermolecular [2 + 2] Cycloaddition of Unactivated Allenes and Alkynes with Unusual Regioselectivity.
作者信息
Zhang Chaoshen, Sung Herman H Y, Williams Ian D, Wu Yun-Dong, Sun Jianwei
机构信息
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR 999077, China.
Shenzhen Bay Laboratory, Shenzhen 518132, China.
出版信息
J Am Chem Soc. 2025 Sep 17;147(37):33350-33358. doi: 10.1021/jacs.5c11285. Epub 2025 Sep 8.
Described here is an efficient protocol for intermolecular [2 + 2] cycloaddition of unactivated and unsymmetrical allenes and alkynes with unusual regioselectivity, counterintuitively favoring the most hindered isomer. CpRu(MeCN)PF served as a uniquely effective catalyst, providing diverse 3-alkylidenecyclobutenes with a broad scope and good functional group compatibility. Both experiments and DFT studies provided important insights into the mechanism, particularly the unusual regioselectivity.
本文描述了一种高效的分子间[2 + 2]环加成反应方案，该反应涉及未活化的不对称丙二烯和炔烃，具有不寻常的区域选择性，与直觉相反，更倾向于位阻最大的异构体。CpRu(MeCN)PF作为一种独特有效的催化剂，可提供多种3-亚烷基环丁烯，适用范围广且官能团兼容性良好。实验和密度泛函理论（DFT）研究都为反应机理提供了重要见解，特别是这种不寻常的区域选择性。
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