Fu Junkai, Shen Hongjuan, Chang Yuanyuan, Li Chuangchuang, Gong Jianxian, Yang Zhen
Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055 (China).
Chemistry. 2014 Sep 26;20(40):12881-8. doi: 10.1002/chem.201403756. Epub 2014 Aug 21.
A 4-substituted-1-tosyl-1,2,3-triazole-based stereoselective synthesis of structurally diverse oxaspirocycles is reported. The synthesis involves Rh-catalyzed loss of nitrogen from 4-substituted-1-tosyl-1,2,3-triazoles, Grignard reaction, and a ring-closing metathesis reaction as key steps. By employing readily available and stable 4-substituted-1-tosyl-1,2,3-triazoles as surrogates of diazo compounds and nitrogen sources, two types of oxaspirocycles were obtained. The latter compounds, which contain adjacent nitrogen stereocenters, could serve as the core structures of many natural products. This chemistry has been successfully applied to the total syntheses of (±)-tuberostemospiroline and (±)-stemona-lactam R.
报道了一种基于4-取代-1-甲苯磺酰基-1,2,3-三唑的立体选择性合成结构多样的氧杂螺环化合物的方法。该合成方法涉及铑催化4-取代-1-甲苯磺酰基-1,2,3-三唑脱氮、格氏反应和闭环复分解反应作为关键步骤。通过使用易于获得且稳定的4-取代-1-甲苯磺酰基-1,2,3-三唑作为重氮化合物和氮源的替代物，获得了两种类型的氧杂螺环化合物。后一类化合物含有相邻的氮立体中心，可作为许多天然产物的核心结构。这种化学方法已成功应用于(±)-块茎螺环碱和(±)-百部酰胺R的全合成。
