Jacquemot Guillaume, Maertens Gaëtan, Canesi Sylvain
Département de chimie, Université du Québec à Montréal, Laboratoire de Méthodologie et Synthèse de Produits Naturels, C.P. 8888, Succ. Centre-Ville, Montréal, H3C 3P8, Québec (Canada), Fax: (+1) 514-987-4054.
Chemistry. 2015 May 18;21(21):7713-5. doi: 10.1002/chem.201500185. Epub 2015 Apr 1.
Althought there are several reported synthetic routes to strychnine, one of the most widely recognized alkaloids, we report an unexplored route with an oxidative dearomatizing process mediated by hypervalent iodine as the key step. The new syntheses of isostrychnine and strychnine have been achieved from an readily available phenol in nine and ten steps. In addition to the key step, these syntheses involve an aza Michael-ether-enol tandem transformation, two heck type cyclizations, a reductive isomerization, and a double reductive amination in cascade leading to the alkaloid main core.
尽管有几种已报道的士的宁（一种最广为人知的生物碱）的合成路线，但我们报道了一条未被探索的路线，该路线以高价碘介导的氧化脱芳构化过程为关键步骤。从一种易得的苯酚出发，分别经过九步和十步反应实现了异士的宁和士的宁的新合成。除关键步骤外，这些合成还涉及氮杂迈克尔-醚-烯醇串联转化、两次赫克型环化、一次还原异构化以及级联双还原胺化反应，从而形成生物碱的主要核心结构。
