Savary David, Baudoin Olivier
Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.
Angew Chem Int Ed Engl. 2021 Mar 1;60(10):5136-5140. doi: 10.1002/anie.202013303. Epub 2021 Jan 14.
C-H activation-based ring-forming methods are a powerful approach for the construction of complex molecular architectures, especially those containing a congested stereocenter. Therefore, this strategy seems perfectly suited to address the synthesis of chiral polycyclic aromatic hydrocarbons (PAHs) and bowl-shaped molecules, which are important target molecules in the field of organic electronic materials. Herein, we describe an enantioselective Pd -catalyzed C(sp )-H arylation protocol for the synthesis of chiral fluoradenes and other warped molecules, which could serve to the bottom-up construction of chiral PAHs. The current approach relies on the use of chiral bifunctional phosphine-carboxylate ligands and delivers diverse polycyclic compounds in high yield and with good to excellent enantioselectivity. The chiroptical properties of the obtained products were investigated, and some of them were found to have a strong ellipticity and an emission band located in the visible region.
基于C-H活化的成环方法是构建复杂分子结构的有力手段，尤其适用于构建含有拥挤立体中心的分子结构。因此，该策略似乎非常适合用于合成手性多环芳烃（PAHs）和碗状分子，这些都是有机电子材料领域的重要目标分子。在此，我们描述了一种对映选择性钯催化的C(sp)-H芳基化方法，用于合成手性芴及其他扭曲分子，这可用于从下而上构建手性PAHs。目前的方法依赖于使用手性双功能膦-羧酸盐配体，能够以高收率和良好至优异的对映选择性提供多种多环化合物。对所得产物的手性光学性质进行了研究，发现其中一些具有很强的椭圆率和位于可见光区域的发射带。
