ACS Chem Biol. 2013 May 17;8(5):877-83. doi: 10.1021/cb300614c. Epub 2013 Feb 22.
We report 12 cyanobactin cyclic peptides, the aestuaramides, from the cultivated cyanobacterium Lyngbya aestuarii. We show that aestuaramides are synthesized enzymatically as reverse O-prenylated tyrosine ethers that subsequently undergo a Claisen rearrangement to produce forward C-prenylated tyrosine. These results reveal that a nonenzymatic Claisen rearrangement dictates isoprene regiochemistry in a natural system. They also reveal one of the mechanisms that organisms use to generate structurally diverse compound libraries starting from simple ribosomal peptide pathways (RiPPs).
我们从培养的蓝藻 Lyngbya aestuarii 中报告了 12 种氰基肽环肽，即 aestuaramides。我们表明，aestuaramides 是作为反式 O-异戊烯基酪氨酸醚酶促合成的，然后进行 Claisen 重排以产生正向 C-异戊烯基酪氨酸。这些结果表明，非酶促 Claisen 重排决定了天然体系中异戊二烯的区域化学。它们还揭示了生物体从简单的核糖体肽途径（RiPPs）开始生成结构多样的化合物文库的机制之一。
