Metal-Free Reaction of ortho-Carbonylated Alkynyl-Substituted Arylaldehydes with Common Amines: Selective Access to Functionalized Isoindolinone and Indenamine Derivatives
Metal-Free Reaction of ortho-Carbonylated Alkynyl-Substituted Arylaldehydes with Common Amines: Selective Access to Functionalized Isoindolinone and Indenamine Derivatives
复制标题
邻位羰基化炔基取代芳醛与常见胺的无金属反应：选择性获得功能化异吲哚酮和茚胺衍生物
DOI：
10.1002/chem.201603045
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发表时间：
2016-11-01
影响因子：
4.3
通讯作者：
You, Jinmao
中科院分区：
文献类型：
--
作者：
Cao, Ziping;Zhu, Hongbo;You, Jinmao
在此，我们描述了一种邻位羰基化的炔基取代芳醛与常见伯胺的反应，该反应能够以高产率提供功能化的异吲哚啉酮和3 - 羟基茚胺产物。根据伯胺取代基的大小，可选择性地采用两种不同的反应途径，即初始的氮杂共轭加成随后进行氢转移以得到异吲哚啉酮骨架，以及独特的氧杂共轭加成随后进行佩塔西斯 - 费里尔重排以生成茚胺衍生物。在三乙胺存在的情况下，小位阻伯胺的反应性质发生改变，能够高效地生成3 - 羟基茚胺衍生物。这些产物含有许多天然产物和生物活性分子中存在的有趣子结构。该反应的特点包括使用无过渡金属催化剂、操作简单、底物范围广泛以及产物多样。
Herein we describe a reaction of ortho-carbonylated alkynyl-substituted arylaldehydes with common primary amines that can provide functionalized isoindolinone and 3-hydroxylindenamine products in high yields. Depending on the substituent size of primary amines, two distinct reaction pathways were exploited selectively, that are, an initial aza-conjugate addition followed by hydrogen transfer to access isoindolinone framework and a unique oxa-conjugate addition followed by Petasis-Ferrier rearrangement to afford indenamine derivatives. In the presence of Et3N, the reaction property of small primary amines was changed, proceeding to afford 3-hydroxylindenamine derivatives efficiently. These products contain interesting substructures that exist in many natural products and bioactive molecules. The reaction features contain the use of transition-metal-free catalysts, simple operation, broad substrate scope, and product diversity.