Institute of Organic Chemistry, Saarland University, P.O. Box 151150, 66041 Saarbrücken, Germany.
Org Biomol Chem. 2018 May 9;16(18):3464-3472. doi: 10.1039/c8ob00391b.
Chelate enolate Claisen rearrangements are powerful reactions for constructing amino acid scaffolds. They generally proceed via chair-like transition states with excellent transfer of stereogenic information. Utilizing this reaction in natural product synthesis gives access to non-proteinogenic amino acids such as (2S,9S)-2-amino-8-oxo-9,10-epoxydecanoic acid (Aoe), the unusual amino acid of a series of histone deacetylase inhibitors (HDACi). Herein the first total synthesis of Cyl-1, a cyclotetrapeptide from Cylindrocladium scoparium, is described.
螯合烯醇酯 Claisen 重排反应是构建氨基酸支架的有力反应。它们通常通过具有出色立体信息转移的椅式过渡态进行。在天然产物合成中利用该反应可以获得非蛋白质氨基酸，如（2S，9S）-2-氨基-8-氧代-9,10-环氧癸酸（Aoe），这是一系列组蛋白去乙酰化酶抑制剂（HDACi）的特殊氨基酸。本文首次报道了来自旋孢腔菌的环四肽 Cyl-1 的全合成。
