Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan.
Org Lett. 2008 Dec 4;10(23):5457-60. doi: 10.1021/ol802225g.
A new route to (-)-agelastatin A is reported. The requisite nitrogen functionalities of the agelastatin core have been installed by intramolecular aziridination of an azidoformate and subsequent regioselective azidation, leading to net trans-diamination of the double bond. The present synthesis also demonstrates two new protocols for the preparation of an imidazolidinone hemiaminal motif from an oxazolidinone intermediate which comprise sequential N-tert-butoxycarbonylation, urea formation, hydrolysis, and oxidative cyclization, and direct aminolysis and subsequent oxidative cyclization.
报道了一种合成 (-)-agelastatin A 的新方法。通过叠氮甲酸酯的分子内环氧化和随后的区域选择性叠氮化，在 agelastatin 核心中引入了所需的氮官能团，从而导致双键的净反式二胺化。本合成还展示了两种从恶唑烷酮中间体制备咪唑烷酮半缩醛基序的新方法，包括顺序的 N-叔丁氧羰基化、脲形成、水解和氧化环化，以及直接氨解和随后的氧化环化。
