Bioinspired total synthesis of boneratamides A-C
Bioinspired total synthesis of boneratamides A-C
复制标题
骨酰胺 A-C 的仿生全合成
DOI：
10.1039/d2ob00486k
复制
发表时间：
2022
影响因子：
3.2
通讯作者：
Y. Ichikawa and S. Hosokawa
中科院分区：
文献类型：
--
作者：
K. Ooka;K. Nakanishi;Y. Udagawa;Y. Ichikawa and S. Hosokawa
我们公开了海洋天然产物 (+)-boneratamide A 的首次合成，其结构由通过酰胺键与焦谷氨酸部分连接的萜烯单元组成。该路线的关键步骤是 (+)-axisonitrile-3 与作为羰基成分的丙酮和 L-谷氨酸的仿生 Ugi 反应。该反应实现了反应组分的非常高效的一锅组装，同时形成 γ-内酰胺环，以 70% 的产率生产 (+)-博那酰胺 A。 (+)-Boneratamide B 和 (–)-boneratamide C 甲酯也使用类似的生物启发策略合成，并使用 X 射线分析阐明了这些物质的立体中心的相对立体化学。
We disclose the first synthesis of the marine natural product, (+)-boneratamide A, whose structure is composed of a terpene unit linked via an amide bond to a pyroglutamic acid moiety. The key step in this route is a bioinspired Ugi reaction of (+)-axisonitrile-3 with acetone as the carbonyl component and L-glutamic acid. This reaction brings about a remarkably efficient, one-pot assembly of reaction components concomitant with γ-lactam ring formation to produce (+)-boneratamide A in 70% yield. (+)-Boneratamide B and (–)-boneratamide C methyl esters were also synthesized using a similar bioinspired strategy, and the relative stereochemistries at the stereogenic centers in these substances were elucidated using X-ray analysis.