Michelliza Sophie, Al-Mourabit Ali, Gateau-Olesker Alice, Marazano Christian
Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette, France.
J Org Chem. 2002 Sep 6;67(18):6474-8. doi: 10.1021/jo025650v.
A new convergent and unified synthesis of the marine natural alkaloid haliclamine A is described. The synthesis of 3-alkylpyridine monomers 8 and 9 was first achieved from a common thiophene intermediate 5. These syntheses make use of thiophene chemistry and the ability of cyclopropylcarbinols 20 and 21 to rearrange to the homoallylic bromides 22 and 23, respectively. The Zincke procedure for the synthesis of pyridinium salts was then applied to the corresponding amino derivatives 8 and 9 to give efficiently unsymmetrical bis-pyridinium macrocycle 1, whose reduction afforded haliclamine A.
本文描述了海洋天然生物碱哈利克拉明A的一种新的汇聚式统一合成方法。首先从常见的噻吩中间体5实现了3-烷基吡啶单体8和9的合成。这些合成利用了噻吩化学以及环丙基甲醇20和21分别重排为高烯丙基溴22和23的能力。然后将用于合成吡啶鎓盐的津克方法应用于相应的氨基衍生物8和9，以高效地得到不对称双吡啶鎓大环化合物1，其还原得到哈利克拉明A。
