Abstract

Although chirality has been recognized as an essential entity for life, it still remains a big mystery how the homochirality in nature emerged in essential biomolecules. Certain achiral motifs are known to assemble into chiral nanostructures. In rare cases, their absolute geometries are enantiomerically biased by mirror symmetry breaking. Here we report the first example of asymmetric catalysis by using a mirror symmetry-broken helical nanoribbon as the ligand. We obtain this helical nanoribbon from a benzoic acid appended achiral benzene-1,3,5-tricarboxamide by its helical supramolecular assembly and employ it for the Cu2+-catalyzed Diels–Alder reaction. By thorough optimization of the reaction (conversion: > 99%, turnover number: ~90), the enantiomeric excess eventually reaches 46% (major/minor enantiomers = 73/27). We also confirm that the helical nanoribbon indeed carries helically twisted binding sites for Cu2+. Our achievement may provide the fundamental breakthrough for producing optically active molecules from a mixture of totally achiral motifs.

Details

Title
Asymmetric catalysis mediated by a mirror symmetry-broken helical nanoribbon
Author
Shen, Zhaocun 1   VIAFID ORCID Logo  ; Sang, Yutao 2   VIAFID ORCID Logo  ; Wang, Tianyu 3   VIAFID ORCID Logo  ; Jiang, Jian 4 ; Meng, Yan 2 ; Jiang, Yuqian 4 ; Kou Okuro 5   VIAFID ORCID Logo  ; Takuzo Aida 6   VIAFID ORCID Logo  ; Liu, Minghua 7   VIAFID ORCID Logo 

 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, P. R. China; Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Tokyo, Japan; University of Chinese Academy of Sciences, Beijing, P. R. China 
 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, P. R. China; University of Chinese Academy of Sciences, Beijing, P. R. China 
 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, P. R. China 
 CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, P. R. China 
 Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Tokyo, Japan 
 Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Tokyo, Japan; RIKEN Center for Emergent Matter Science, Saitama, Japan 
 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, P. R. China; University of Chinese Academy of Sciences, Beijing, P. R. China; CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, P. R. China; Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, P. R. China 
Pages
1-8
Publication year
2019
Publication date
Sep 2019
Publisher
Nature Publishing Group
e-ISSN
20411723
Source type
Scholarly Journal
Language of publication
English
ProQuest document ID
2284582893
Copyright
© 2019. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.