Tanaka Satomi, Shiomi Shinya, Ishikawa Hayato
Department of Chemistry, Graduate School of Science and Technology, Kumamoto University , 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
J Nat Prod. 2017 Aug 25;80(8):2371-2378. doi: 10.1021/acs.jnatprod.7b00464. Epub 2017 Aug 13.
Isoprene units derived from dimethylallyl diphosphate (DMAPP) are an important motif in many natural products including terpenoids, carotenoids, steroids, and natural rubber. Understanding the chemical characteristics of DMAPP is an important topic in natural products chemistry, organic chemistry, and biochemistry. We have developed a direct bioinspired indole prenylation reaction using DMAPP or its equivalents as the electrophile in homogeneous aqueous acidic media in the absence of enzyme to provide prenylated indole products. After establishing the bioinspired indole prenylation reaction, this was then used to achieve the synthesis of a series of natural products, namely, N-prenylcyclo-l-tryptophyl-l-proline, tryprostatins, rhinocladins, and terezine D.
来源于二甲基烯丙基二磷酸（DMAPP）的异戊二烯单元是许多天然产物中的重要结构基元，包括萜类化合物、类胡萝卜素、甾体和天然橡胶。了解DMAPP的化学特性是天然产物化学、有机化学和生物化学中的一个重要课题。我们开发了一种直接的仿生吲哚异戊烯基化反应，在无酶的均相酸性水介质中使用DMAPP或其等效物作为亲电试剂，以提供异戊烯基化吲哚产物。在建立了仿生吲哚异戊烯基化反应之后，该反应随后被用于实现一系列天然产物的合成，即N-异戊烯基环-L-色氨酰-L-脯氨酸、色曲菌素、鼻枝菌素和特瑞嗪D。
