Oh Sang-Ha, Oh Joo-Yeon, Vo Ngoc Binh, Ngo Quoc Anh, Kovalenko Vitaly, Cho Cheon-Gyu
Center for New Directions in Organic Synthesis, Department of Chemistry, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763, Korea.
Institute of Chemistry, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay, Ha Noi 00000, Vietnam.
J Org Chem. 2024 Sep 20;89(18):13501-13510. doi: 10.1021/acs.joc.4c01696. Epub 2024 Aug 31.
A new asymmetric synthetic route to (+)- and (-)-limaspermidine was devised, starting with chirally resolved enantiomerically pure 2-pyrone Diels-Alder cycloadducts. This route utilizes intramolecular Pd-catalyzed aromatic C-H amidation and imino-Diels-Alder reactions to construct the key indoline and indolizidine subunits onto the central cyclohexane core, allowing the straightforward formal total syntheses of both (+)- and (-)-limaspermidine.
设计了一条合成(+)-和(-)-利马斯珀米定的新的不对称合成路线，该路线从手性拆分的对映体纯的2-吡喃酮狄尔斯-阿尔德环加成物开始。此路线利用分子内钯催化的芳族C-H酰胺化反应和亚氨基-狄尔斯-阿尔德反应，在中心环己烷核心上构建关键的二氢吲哚和吲哚里西啶亚基，从而能够直接对(+)-和(-)-利马斯珀米定进行形式上的全合成。
