Chiral Supramolecular U-Shaped Catalysts Induce the Multiselective Diels-Alder Reaction of Propargyl Aldehyde
Chiral Supramolecular U-Shaped Catalysts Induce the Multiselective Diels-Alder Reaction of Propargyl Aldehyde
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DOI：
10.1021/jacs.8b09974
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发表时间：
2018-11-28
影响因子：
15
通讯作者：
Ishihara, Kazuaki
中科院分区：
文献类型：
--
作者：
Hatano, Manabu;Sakamoto, Tatsuhiro;Ishihara, Kazuaki
Diels-Alder 反应是一种传统的 [4 + 2] 环加成反应，具有两个碳碳键的形成，是合成多功能且独特的六元环的最强大的工具之一。我们发现手性超分子U型硼路易斯酸催化剂促进了炔丙醛与环状二烯前所未有的多选择性狄尔斯阿尔德反应。独立于底物控制，对映选择性、内/外选择性、π面选择性、区域选择性、位点选择性和底物选择性可以通过本发明的U形催化剂来控制。所得反应产物可用于手性二烯配体和(+)-沙可霉素关键中间体的简洁合成。这里提出的结果可能部分有助于开发用于多选择性反应的人工酶类超分子催化剂，该催化剂将能够靶向迄今为止无法合成的有机化合物。
The Diels-Alder reaction, which is a traditional [4 + 2] cycloaddition with two carbon carbon bond formations, is one of the most powerful tools to synthesize versatile and unique six-membered rings. We show that chiral supramolecular U-shaped boron Lewis acid catalysts promote the unprecedented multiselective Diels Alder reaction of propargyl aldehyde with cyclic dienes. Independent from the substrate control, enantio-, endo/exo-, pi-facial-, regio-, site-, and substrate-selectivities could be controlled by the present U-shaped catalysts. The obtained reaction products could access the concise synthesis of chiral diene ligands and a key intermediate of (+)-sarkomycin. The results presented here might partially contribute to the development of artificial enzyme-like supramolecular catalysts for multiselective reactions, which will be able to target organic compounds that have thus far eluded synthesis.