Siloxacyclopentenes as Dienophile-Linked Directing Groups in Intramolecular Diels-Alder Reactions
Siloxacyclopentenes as Dienophile-Linked Directing Groups in Intramolecular Diels-Alder Reactions
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DOI：
10.1021/ol802266s
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发表时间：
2008-11-20
期刊：
影响因子：
5.2
通讯作者：
Roush, William R.
中科院分区：
文献类型：
--
作者：
Halvorsen, Geoff T.;Roush, William R.
描述了三烯 5 和 6 与受硅氧烷环戊烯约束的亲二烯体的合成和分子内 Diels-Alder 反应。这些反应提供了具有高非对映选择性的初级环加合物7和8。这些环加合物在环稠合质子和相邻的 C(1) 烷氧基之间具有反式关系，并且可以根据取代基 R 进一步加工成醇 9 和 11（通过原硫脱甲硅烷基化）或 10 和 12（通过 Fleming-Tamao 氧化）。
The synthesis and intramolecular Diels-Alder reactions of trienes 5 and 6 with a siloxacyclopentene-constrained dienophile are described. These reactions provide the primary cycloadducts 7 and 8 with high diastereoselectivity. These cycloadducts possess trans-relationships between the ring fusion proton and the adjacent C(1) alkoxy group and can be further elaborated to alcohols 9 and 11 (via protiodesilylation) or to 10 and 12 (via Fleming-Tamao oxidation) depending on the substitutent R.