Nishikawa Toshio, Urabe Daisuke, Yoshida Kazumasa, Iwabuchi Tomoko, Asai Masanori, Isobe Minoru
Laboratory of Organic Chemistry, Graduate School of Bioagricultural Sciences, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
Chemistry. 2004 Jan 23;10(2):452-62. doi: 10.1002/chem.200305111.
8,11-Dideoxytetrodotoxin, an unnatural tetrodotoxin analogue, was synthesized in a highly stereoselective manner from a common intermediate from our synthetic studies on tetrodotoxin. The key features in the synthesis were as follows: neighboring group participation of a trichloroacetamide to allow regioselective and stereoselective hydroxylation, protection of a delta-hydroxylactone as an ortho ester, and guanidine installation through the use of Boc-protected isothiourea. Global deprotection of the fully protected intermediate under acidic conditions gave 8,11-dideoxytetrodotoxin, which exhibited very weak biological activities.
8,11-二脱氧河豚毒素，一种非天然的河豚毒素类似物，以高度立体选择性的方式从我们对河豚毒素合成研究中的一个共同中间体合成。该合成的关键特征如下：三氯乙酰胺的邻基参与以实现区域选择性和立体选择性羟基化，将δ-羟基内酯保护为原酸酯，以及通过使用Boc保护的异硫脲安装胍基。在酸性条件下对完全保护的中间体进行全局脱保护得到8,11-二脱氧河豚毒素，其表现出非常弱的生物活性。
