Chen Peiqi, Yang Hesi, Zhang Hao, Chen Wei, Zhang Zheng, Zhang Jing, Li Huilin, Wang Xiaolei, Xie Xingang, She Xuegong
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P.R. China.
Org Lett. 2020 Mar 6;22(5):2022-2025. doi: 10.1021/acs.orglett.0c00399. Epub 2020 Feb 25.
The first total synthesis of oxindole alkaloid (-)-gardmultimine A has been achieved in 19 steps from d-tryptophan in a fully stereocontrolled manner. This synthesis features (1) an Ir-catalyzed regioselective C-H borylation/oxidation sequence to introduce the C12 methoxyl group, (2) a stereocontrolled oxidative rearrangement of indole to construct the spirooxindole motif, and (3) an Au(I)-catalyzed transannular Conia-ene-type cyclization to establish the azabicyclo[2.2.2]octane skeleton and the exocyclic -alkene with exclusive stereoselectivity.
以d-色氨酸为原料，经19步全立体控制合成实现了吲哚酮生物碱（-）-gardmultimine A的首次全合成。该合成方法的特点包括：（1）通过铱催化的区域选择性C-H硼化/氧化序列引入C12甲氧基；（2）吲哚的立体控制氧化重排以构建螺吲哚酮基序；（3）金（I）催化的跨环柯尼雅-烯型环化反应，以专一的立体选择性构建氮杂双环[2.2.2]辛烷骨架和环外烯烃。
