Asymmetric modular synthesis of highly functionalized medium-sized carbocycles and lactones via ring-closing metathesis of sulfoximine-substituted trienes.
Asymmetric modular synthesis of highly functionalized medium-sized carbocycles and lactones via ring-closing metathesis of sulfoximine-substituted trienes.
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DOI：
10.1002/chin.200715062
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发表时间：
2006-11
影响因子：
15
通讯作者：
M. Lejkowski;H. Gais;Prabal Banerjee;C. Vermeeren
中科院分区：
文献类型：
--
作者：
M. Lejkowski;H. Gais;Prabal Banerjee;C. Vermeeren
已开发出中等大小碳环和内酯的模块化不对称合成，可提供高度取代的 7、9 和 11 元环。关键步骤是（1）由烯丙亚砜亚胺和不饱和以及饱和醛高度非对映选择性合成亚砜亚胺取代的高烯丙醇，（2）亚砜亚胺取代的烯基锂衍生物的E-立体选择性烷基化和羟烷基化，（3）亚砜亚胺取代的高烯丙醇的酯化，以及（4）亚砜亚胺取代的三烯与钌催化剂8。提供了进一步合成亚砜亚胺取代的碳环的两个例子。在三乙基甲硅烷基存在下，12的叔丁基二甲基甲硅烷基选择性裂解，得到烯丙醇18，烯丙醇18被氧化成烯酮19。亚砜亚胺取代的碳环9与LiCuMe2发生交叉偶联反应，得到甲基取代的衍生物20。
A modular asymmetric synthesis of medium-sized carbocycles and lactones has been developed that affords highly substituted 7-, 9-, and 11-membered rings. The key steps are (1) the highly diastereoselective synthesis of sulfoximine-substituted homoallylic alcohols from allylic sulfoximines and unsaturated as well as saturated aldehydes, (2) an E-stereoselective alkylation and hydroxyalkylation of sulfoximine-substituted alkenyllithium derivatives, (3) the esterification of sulfoximine-substituted homoallylic alcohols, and (4) the ring-closing metathesis reaction of sulfoximine-substituted trienes with the ruthenium catalyst 8. Two examples for the further synthetic elaboration of the sulfoximine-substituted carbocycles are provided. The selective cleavage of the tert-butyldimethylsilyl group of 12 in the presence of the triethylsilyl group afforded the allylic alcohol 18 which was oxidized to enone 19. A cross-coupling reaction of the sulfoximine-substituted carbocycle 9 with LiCuMe2 furnished the methyl-substituted derivative 20.