Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation of Dihydroquinolinones
Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation of Dihydroquinolinones
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DOI：
10.1021/acs.orglett.9b00358
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发表时间：
2019-03-15
期刊：
影响因子：
5.2
通讯作者：
Hull, Kami L.
中科院分区：
文献类型：
--
作者：
Trost, Barry M.;Nagaraju, Anugula;Hull, Kami L.
公开了一种钯催化的苯并融合和非苯并融合s -戊内酯的脱羧不对称烯丙基烷基化反应（Pd-DAAA）。这种方法可以获得具有c3 -季立体中心的手性内酰胺，这是许多天然产物和生物活性化合物的核心。该反应通过钯催化的烯丙基酯电离进行，随后二氧化碳挤压并将亲电的pd -pi-烯丙基配合物与原位生成的内酰胺烯醇酯重新组合。最后一步将外消旋烯丙基酯原料转化为具有高产率和对映体过剩的对映体富集的取代内酰胺。
A palladium-catalyzed decarboxylative asymmetric allylic alkylation (Pd-DAAA) of benzo-fused and non-benzo-fused S-valerolactams is disclosed. This methodology gives access to chiral lactams bearing C3-quaternary stereo-centers, which are central to many natural products and biologically active compounds. The reaction proceeds via palladium-catalyzed ionization of an allyl ester, followed by carbon dioxide extrusion and recombination of the electrophilic Pd-pi-allyl complex with the in situ generated lactam enolate. This final step converts racemic allylic ester starting materials into enantiomerically enriched substituted lactams with high yield and enantiomeric excess.