Masuda Ryosuke, Kuwano Satoru, Goto Kei
Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
J Org Chem. 2021 Nov 5;86(21):14433-14443. doi: 10.1021/acs.joc.1c01252. Epub 2021 Sep 1.
Late-stage functionalization of the periphery of oligophenylene dendrimers was efficiently achieved via site-selective C-H activation of a preconstructed, readily accessible dendron. By fourfold iridium-catalyzed C-H borylation followed by Suzuki-Miyaura cross-coupling, various arene units were introduced into the end points of the 1,3,5-phenylene-based hydrocarbon dendron. Coupling of the modified dendrons with a core unit, such as 2,6-dibromobenzoic acid derivatives, afforded the periphery-functionalized dendrimers that also have an endohedral functionality at the core position.
通过对预先构建的、易于获得的树枝单元进行位点选择性C-H活化，高效实现了低聚苯撑树枝状聚合物外围的后期功能化。通过四倍铱催化的C-H硼化反应，随后进行铃木-宫浦交叉偶联反应，将各种芳烃单元引入到基于1,3,5-亚苯基的烃树枝单元的端点。将修饰后的树枝单元与核心单元（如2,6-二溴苯甲酸衍生物）偶联，得到了外围功能化的树枝状聚合物，其在核心位置也具有内面功能。
