Bronsted Acid-Catalyzed Intramolecular α-Arylation of Ketones with Phenolic Nucleophiles via Oxy-Allyl Cation Intermediates
Bronsted Acid-Catalyzed Intramolecular α-Arylation of Ketones with Phenolic Nucleophiles via Oxy-Allyl Cation Intermediates
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DOI：
10.1002/ejoc.202000169
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发表时间：
2020-03-31
影响因子：
2.8
通讯作者：
Maruoka, Keiji
中科院分区：
文献类型：
--
作者：
Aota, Yusuke;Doko, Yuki;Maruoka, Keiji
氧烯丙基阳离子中间体的亲核加成已成为羰基化合物α位置的一种很有前途的功能化方法。然而，可用于捕获催化生成的氧烯丙基阳离子的碳亲核试剂的结构仅限于高亲核试剂。在此，我们报道了Bronsted酸催化的酮的α -芳基化，在氧烯丙基阳离子催化中，使用较少探索的酚类亲核试剂作为碳亲核试剂，使酮在α位置具有全碳季中心。
Nucleophilic addition to the oxy-allyl cation intermediate has emerged as a promising methodology for functionalization of the alpha-position of carbonyl compounds in an umpolung fashion. However, a structure of available carbon nucleophiles to trap the catalytically generated oxy-allyl cation has been limited to highly nucleophilic ones. Herein, we report the Bronsted acid-catalyzed alpha-arylation of ketones employing less explored phenolic nucleophiles as carbon nucleophiles in the oxy-allyl cation catalysis, affording ketones bearing an all carbon quaternary center at the alpha-position.