Shiozuka Akira, Sekine Kohei, Toki Takumi, Kawashima Kyohei, Mori Toshifumi, Kuninobu Yoichiro
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasugakoen, Kasuga-shi, Fukuoka 816-8580, Japan.
Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen, Kasuga-shi, Fukuoka 816-8580, Japan.
Org Lett. 2022 Jun 17;24(23):4281-4285. doi: 10.1021/acs.orglett.2c01663. Epub 2022 Jun 5.
We have developed the divergent deaminative borylation and hydrodeamination of primary aromatic amines using bis(pinacolato)diboron. These transformations can be switched by the reaction conditions. Mechanistic and computational studies have suggested that the cleavage of the C-N bond and the formation of C-B bond are unlikely to involve free aryl radical intermediates. However, hydrodeamination is shown to proceed via hydrogen atom transfer between the corresponding aryl radical and an ethereal solvent.
我们利用双(频哪醇合)二硼开发了伯芳香胺的发散性脱氨基硼化和加氢脱氨基反应。这些转化反应可以通过反应条件进行切换。机理和计算研究表明，C-N键的断裂和C-B键的形成不太可能涉及游离芳基自由基中间体。然而，加氢脱氨基反应显示是通过相应芳基自由基与醚类溶剂之间的氢原子转移进行的。
