CAS Key Lab of High-Performance Synthetic Rubber and Its Composite Materials , Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street , Changchun , Jilin 130022 , China.
The University of Chinese Academy of Sciences , Beijing 100864 , China.
J Org Chem. 2019 Nov 1;84(21):13890-13896. doi: 10.1021/acs.joc.9b02054. Epub 2019 Oct 2.
A new synthetic route for a short synthesis of (±)-leuconodines D and E was developed. The rapid construction of the diaza[5.5.6.6]fenestrane core was achieved through a sequence involving a Pd-catalyzed aerobic oxidative Heck cross-coupling reaction for the construction of indole δ-lactam containing a full-carbon quaternary center, an epoxidative cyclization for the assembly of pyrroloindole, and a ring-closing metathesis for the construction of the piperidine ring. As a result, the total synthesis of (±)-leuconodine E () was achieved for the first time within a 10-step linear sequence, and a more concise total synthesis of (±)-leuconodine D () was accomplished within a 12-step linear sequence from the commercially available tryptophol.
开发了一条（±）-leuconodines D 和 E 的短合成新路线。通过一系列反应，包括 Pd 催化的有氧氧化 Heck 交叉偶联反应构建含全碳季碳原子的吲哚 δ-内酰胺、环氧化环化构建吡咯并吲哚以及闭环复分解反应构建哌啶环，快速构建了 diaza[5.5.6.6]fenestrane 核心。结果，（±）-leuconodine E () 的全合成首次在 10 步线性序列中实现，并且从商业可得的色氨酸出发，通过 12 步线性序列完成了（±）-leuconodine D () 的更简洁的全合成。
