Wang Donglei, Shao Ying-Bo, Chen Yunrong, Xue Xiao-Song, Yang Xiaoyu
School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, P. R. China.
College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
Angew Chem Int Ed Engl. 2022 May 23;61(22):e202201064. doi: 10.1002/anie.202201064. Epub 2022 Mar 30.
An efficient approach for asymmetric synthesis of planar-chiral macrocycles (paracyclophanes) has been disclosed through enantioselective electrophilic aromatic aminations with azodicarboxylates enabled by chiral phosphoric acid catalysis. A wide range of chiral macrocycles bearing varied ring sizes (16 to 23-membered) and functional group-containing ansa chains were readily afforded using this method, with excellent yields and high enantioselectivities (23 examples, up to 99.5 : 0.5 er). Experimental studies and DFT calculations were performed to elucidate the mechanism and origin of stereoselectivities of these reactions. Preliminary utilization of the planar-chiral macrocycle as chiral organocatalyst showcased the potential applications of these novel chiral skeletons.
通过手性磷酸催化的对映选择性亲电芳香胺化反应，实现了一种高效合成平面手性大环化合物（对环芳烷）的方法。利用该方法可以轻松得到一系列具有不同环大小（16至23元）和含官能团桥链的手性大环化合物，产率优异，对映选择性高（23个例子，高达99.5:0.5的对映体比例）。进行了实验研究和密度泛函理论（DFT）计算，以阐明这些反应的立体选择性机理和起源。平面手性大环化合物作为手性有机催化剂的初步应用展示了这些新型手性骨架的潜在应用价值。
