通过carbazate 添加/Peterson 烯烃化方法的全合成细胞毒性烯基腙天然产物肼霉素 A 和 B。

Total synthesis of the cytotoxic enehydrazide natural products hydrazidomycins A and B by a carbazate addition/Peterson olefination approach.

机构信息

Davenport Research Laboratories, Department of Chemistry, University of Toronto , 80 St. George Street, Toronto ON, Canada.

出版信息

Org Lett. 2013 Jun 21;15(12):3086-9. doi: 10.1021/ol401275f. Epub 2013 Jun 4.

DOI:10.1021/ol401275f

PMID:23734814

Abstract

The first total syntheses of two natural antitumor enehydrazide compounds (hydrazidomycins A and B) and a related positional isomer of hydrazidomycin B (elaiomycin B) have been accomplished in a rapid and stereocontrolled fashion using a Peterson elimination approach. A regioselective silyl epoxide ring opening reaction with Boc-carbazate followed by base-mediated Peterson siloxide elimination stereospecifically installed the key Z-enehydrazide functionality. The use of Boc-carbazate allowed for the differential functionalization of the hydrazide nitrogens.

摘要

两种天然抗肿瘤烯酰肼化合物（hydrazidomycins A 和 B）和 hydrazidomycin B 的一个相关位置异构体（elaiomycin B）的首次全合成已经通过 Peterson 消除方法快速且立体控制的方式完成。Boc-碳二亚胺的区域选择性硅醚环开反应，随后通过碱介导的 Peterson 硅氧烷消除，立体特异性地引入了关键的 Z-烯酰肼官能团。Boc-碳二亚胺的使用允许对酰肼氮进行差异官能化。