A Unified Route to the Welwitindolinone Alkaloids: Total Syntheses of (-)-N-Methylwelwitindolinone C Isothiocyanate, (-)-N-Methylwelwitindolinone C Isonitrile, and (-)-3-Hydroxy-N-methylwelwitindolinone C Isothiocyanate

被引：57
作者：
Allan, Kevin M. [1 ]
Kobayashi, Kenichi [1 ]
Rawal, Viresh H. [1 ]
机构：
[1] Univ Chicago, Dept Chem, Chicago, IL 60637 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 03期
关键词：
MULTIPLE-DRUG RESISTANCE; WELWISTATIN; EFFICIENT; KETONES; CORE; FISCHERINDOLES; REARRANGEMENT; HAPALINDOLES; CONSTRUCTION; OXINDOLES;
D O I：
10.1021/ja210793x
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
As part of a comprehensive strategy to the welwitindolinone alkaloids possessing a bicyclo[4.3.1]decane core, we report herein concise asymmetric total syntheses of (-)-N-methylwelwitindolinone C isothiocyanate (2a), (-)-N-methylwelwitindolinone C isonitrile (2b), and (-)-3-hydroxy-N-methylwelwitindolinone C isothiocyanate (3a) from a common tetracyclic intermediate. The crucial vinyl chloride moiety was installed through electrophilic chlorination of a hydrazone, but only after adjustment of reactivity to circumvent a facile skeletal rearrangement. Selective desulfurization and oxidation of 2a provided access to 2b and 3a, respectively. Notably, this work provides corrected H-1 and C-13 NMR spectral data for 3a.
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收藏
页码：1392 / 1395
页数：4
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