Bhunnoo Riaz A, Hobbs Heather, Lainé Dramane I, Light Mark E, Brown Richard C D
The School of Chemistry, University of Southampton, Highfield, Southampton SO171BJ, UK.
Org Biomol Chem. 2009 Mar 7;7(5):1017-24. doi: 10.1039/b813201a. Epub 2009 Jan 28.
A short synthesis of the non-adjacent bis-THF core of the Annonaceous acetogenin cis-sylvaticin (1) is described. C(2) Symmetrical (Z,E,E,Z)- and (E,E,E,E)-tetraenes and were synthesised in six and three steps respectively from (1E,5E,9E)-cyclododeca-1,5,9-triene. Subsequent permanganate promoted asymmetric bi-directional oxidative cyclisation of tetraene was used to create the non-adjacent bis-THF core of 1, installing seven of the nine stereogenic centres present in the natural product in a single step. Desymmetrization of the oxidative cyclisation product by mono-tosylation gave access to a C11-C32 fragment of cis-sylvaticin.
描述了番荔枝科产乙酸菌素顺式西维菌素（1）的非相邻双四氢呋喃核心的简短合成方法。分别以（1E,5E,9E）-环十二碳-1,5,9-三烯为原料，经六步和三步反应合成了C（2）对称的（Z,E,E,Z）-和（E,E,E,E）-四烯。随后利用高锰酸盐促进的四烯不对称双向氧化环化反应构建了1的非相邻双四氢呋喃核心，一步反应就构建了天然产物中九个立体中心中的七个。通过单甲苯磺酰化对氧化环化产物进行去对称化反应，得到了顺式西维菌素的C11-C32片段。
