1. Enantioselective Synthesis of Planar‐Chiral Macrocycles through Asymmetric Electrophilic Aromatic Amination.
- Author
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Wang, Donglei, Shao, Ying‐Bo, Chen, Yunrong, Xue, Xiao‐Song, and Yang, Xiaoyu
- Subjects
AMINATION ,PHOSPHORIC acid ,ASYMMETRIC synthesis ,PARACYCLOPHANES ,CATALYSIS ,STEREOSELECTIVE reactions - Abstract
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. [ABSTRACT FROM AUTHOR]
- Published
- 2022
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