Peng Chuanyong, Wang Chenhong, Wu Changhui, Xing Junhao, Xue Fei, Dou Xiaowei
Department of Chemistry, School of Science, China Pharmaceutical University, Nanjing 211198, People's Republic of China.
Institute of Material Physics and Chemistry, College of Science, Nanjing Forestry University, Nanjing 210037, People's Republic of China.
Org Lett. 2025 Jan 24;27(3):869-873. doi: 10.1021/acs.orglett.4c04612. Epub 2025 Jan 10.
The development and enantioselective synthesis of two types of -symmetric spirobi[dihydrophenalene] structures is reported. The reaction proceeds via rhodium-catalyzed 2-fold asymmetric conjugate arylation of dienones followed by BF·OEt-promoted spirocyclization to give the enantiopure spiro products. Additive-dependent chemodivergent synthesis of 3,3'-diarylated 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diols (3,3'-Ar-SPHENOLs) and the corresponding spiro diary ethers from the same intermediate is achieved. The structural properties of 3,3'-Ph-SPHENOL are analyzed, and its application in asymmetric catalysis has been preliminarily demonstrated.
报道了两种类型的对称螺二氢菲结构的开发及其对映选择性合成。该反应通过铑催化的二烯酮的双不对称共轭芳基化反应，随后经BF·OEt促进的螺环化反应，得到对映体纯的螺环产物。实现了从同一中间体出发，通过添加剂依赖性化学发散合成3,3'-二芳基化的2,2',3,3'-四氢-1,1'-螺二菲-9,9'-二醇（3,3'-Ar-SPHENOLs）和相应的螺二芳基醚。分析了3,3'-Ph-SPHENOL的结构性质，并初步证明了其在不对称催化中的应用。
