Boratyński Przemysław J, Turowska-Tyrk Ilona, Skarzewski Jacek
Department of Organic Chemistry, Faculty of Chemistry, Wrocław University of Technology, 50-370 Wrocław, Poland.
Org Lett. 2008 Feb 7;10(3):385-8. doi: 10.1021/ol7026625. Epub 2008 Jan 8.
A simple and efficient method for the highly stereoselective C-9 arylation and vinylation of Cinchona alkaloids was developed. Both 9S- and 9R-chloroquinine with PhMgBr yielded 9S-phenylquinine (X-ray structure). The reactions with various aryl and vinyl Grignard reagents resulted in the series of 9S-aryl and vinyl alkaloid derivatives. The stereochemical outcome was rationalized by coordination of the magnesium atom to the quinuclidine nitrogen, thus directing the nucleophilic attack at the C-9 stereogenic center.
开发了一种用于金鸡纳生物碱的高度立体选择性C-9芳基化和乙烯基化的简单有效方法。9S-和9R-氯喹宁与苯基溴化镁反应均生成9S-苯基喹宁（X射线结构）。与各种芳基和乙烯基格氏试剂的反应产生了一系列9S-芳基和乙烯基生物碱衍生物。通过镁原子与奎宁环氮的配位使立体化学结果合理化，从而指导亲核进攻C-9立体中心。
