New stereoselective synthesis of 2-allyl-4-nitroalkylpiperidine-2-thiones and their transformation to annulated piperidinones
New stereoselective synthesis of 2-allyl-4-nitroalkylpiperidine-2-thiones and their transformation to annulated piperidinones
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DOI：
10.1055/s-2003-41016
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发表时间：
2003-09-02
期刊：
影响因子：
2
通讯作者：
Sosnicki, JG
中科院分区：
文献类型：
--
作者：
Sosnicki, JG
以哌啶-2-硫酮或市售的2-巯基吡啶为原料，通过硝基烷烃与5,6-二氢吡啶-2-硫酮的迈克尔加成、S-烯丙基化和硫代-克莱森重排，实现了高度立体控制的反式-3-烯丙基-4硝基-烷基-1,6-二取代的δ-硫代内酰胺。通过脱硫获得的相应内酰胺被发现是在区域和立体选择性自由基 5-exo-trig 环化过程中构建转稠合双环 2-哌啶酮衍生物（八氢[2]吡啶酮）的合适前体。
Highly stereocontrolled access to trans-3-allyl-4nitro-alkyl-1,6-disubstituted delta-thiolactams was achieved starting from piperidine-2-thione or commercially available 2-mercaptopyridine via Michael-addition of nitroalkanes to 5,6-dihydropyridin-2-thiones, S-allylation and thio-Claisen rearrangement. The corresponding lactams obtained by desulfurisation, were found to be suitable precursors for the construction of trans-fused bicyclic 2-piperidinone derivatives (octahydro[2]pyrindinones) in a regio- and stereoselective radical 5-exo-trig annulation process.