Graduate School of Pharmaceutical Sciences, Chiba University.
Chem Pharm Bull (Tokyo). 2023;71(8):624-632. doi: 10.1248/cpb.c23-00227.
To develop dearomatization reactions based on a nucleophilic activation of phenols, naphthols, and indoles, ipso-Friedel-Crafts-type C-alkylation must be selectively promoted over competitive O- or N-alkylation reactions. Resolving this chemoselectivity issue is essential for developing this class dearomatization reaction. We found that various dearomatization reactions could be developed using appropriately designed aromatic substrates with an electrophilic moiety for intramolecular reactions. This review describes the transition-metal-catalyzed dearomatization reactions developed by our group. π-Allylpalladium species, η-propargylpalladium species, alkynes activated by Au(I) species, and silver carbene species could be applied as electrophiles in our reaction system, which provided access to a wide variety of dearomatized products from planar aromatic compounds in a highly chemoselective manner.
为了开发基于酚类、萘酚类和吲哚类化合物的亲核活化的去芳构化反应，必须选择性地促进异丙基-弗里德尔-克拉夫茨型 C-烷基化反应，而不是竞争性的 O-或 N-烷基化反应。解决这个化学选择性问题对于开发这类去芳构化反应至关重要。我们发现，使用具有亲电部分的适当设计的芳香底物进行分子内反应，可以开发出各种去芳构化反应。本综述描述了我们小组开发的过渡金属催化的去芳构化反应。π-烯丙基钯物种、η-丙炔基钯物种、金（I）物种活化的炔烃和银卡宾物种可以作为亲电试剂应用于我们的反应体系中，该体系以高度化学选择性的方式，从平面芳香化合物中获得了广泛的去芳构化产物。
