Concise Stereoselective Synthesis of Oxaspirocycles with 1‐Tosyl‐1,2,3‐triazoles: Application to the Total Syntheses of (±)‐Tuberostemospiroline and (±)‐Stemona‐lactam R |
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| Authors: | Junkai Fu Hongjuan Shen Yuanyuan Chang Prof. Dr. Chuangchuang Li Dr. Jianxian Gong Prof. Dr. Zhen Yang |
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| Affiliation: | 1. Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055 (China);2. Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS), Peking‐Tsinghua Center for Life Sciences, Peking University, Beijing 100871 (China) |
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| Abstract: | 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. |
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| Keywords: | carbenes oxaspirocycles sigmatropic rearrangement spiro compounds total synthesis |
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