Practical Electrochemical Anodic Oxidation of Polycyclic Lactams for Late Stage Functionalization

被引:68
作者
Frankowski, Kevin J. [1 ]
Liu, Ruzhang [1 ]
Milligan, Gregory L. [2 ]
Moeller, Kevin D. [3 ]
Aube, Jeffrey [1 ]
机构
[1] Univ Kansas, Dept Med Chem, Lawrence, KS 66047 USA
[2] St Martins Univ, Dept Chem, Lacey, WA 98503 USA
[3] Washington Univ, Dept Chem, St Louis, MO 63130 USA
关键词
anodic oxidation; diversity-oriented synthesis; heterocycles; lactams; N-acyliminium ions; N-ACYLIMINIUM IONS; INTRAMOLECULAR SCHMIDT REACTION; NATURAL-PRODUCT SYNTHESIS; ELECTROORGANIC CHEMISTRY; PROLINE DERIVATIVES; ALKYL AZIDES; CONSTRUCTION; ANALOGS; PEPTIDOMIMETICS; NEOTHRAMYCIN;
D O I
10.1002/anie.201504775
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Electrochemistry provides a powerful tool for the late-stage functionalization of complex lactams. A two-stage protocol for converting lactams, many of which can be prepared through the intramolecular Schmidt reaction of keto azides, is presented. In the first step, anodic oxidation in MeOH using a repurposed power source provides a convenient route to lactams bearing a methoxy group adjacent to nitrogen. Treatment of these intermediates with a Lewis acid in dichloromethane permits the regeneration of a reactive acyliminium ion that is then reacted with a range of nucleophilic species.
引用
收藏
页码:10555 / 10558
页数:4
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