Concise Stereoselective Synthesis of Oxaspirocycles with 1-Tosyl-1,2,3-triazoles: Application to the Total Syntheses of (±)Tuberostemospiroline and (±)-Stemona-lactam

被引：57

作者：

Fu, Junkai ^{[1
]}

Shen, Hongjuan ^{[1
]}

Chang, Yuanyuan ^{[1
]}

Li, Chuangchuang ^{[1
]}

Gong, Jianxian ^{[1
]}

Yang, Zhen ^{[1
,2
,3
]}

机构：

[1] Peking Univ, Shenzhen Grad Sch, Sch Chem Biol & Biotechnol, Lab Chem Genom, Shenzhen 518055, Peoples R China

[2] Peking Univ, Key Lab Bioorgan Chem & Mol Engn, Minist Educ, Beijing 100871, Peoples R China

[3] Peking Univ, BNLMS, Peking Tsinghua Ctr Life Sci, Beijing 100871, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 40期

关键词：

carbenes; oxaspirocycies; sigmatropic rearrangement; spiro compounds; total synthesis; RHODIUM(II) AZAVINYL CARBENES; TERMINAL ALKYNES; CATALYZED TRANSANNULATION; EFFICIENT SYNTHESIS; STEMONA ALKALOIDS; REARRANGEMENT; ANNULATION; 1,2,3-TRIAZOLES; CYCLOADDITIONS; CONSTRUCTION;

D O I：

10.1002/chem.201403756

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 nitro- gen 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.

引用

页码：12881 / 12888

页数：8

共 81 条

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