Inherently Chiral Calixarenes from Catalytic Enantioselective Transannular Arene-Arene Cross-Coupling Reaction

01 November 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Under the catalysis of PdBr2 and a chiral phosphoramidite ligand derived from R-3,3'-bis(trifluoromethyl)-[1,1'-binaphthalene]-2,2'-diol, the upper-rim mono (2-bromoaroyl)-substituted calix[4]arene derivatives underwent facile enantioselective desymmetrization reaction to afford 9H-fluorene-embedded inherently chiral cyclophanes in good yields with ee up to 94%. The transannular arene-arene cross coupling reaction proceeded most probably through an oxidation addition of Caryl-Br bond to ligated palladium catalyst, an unusual long range 1,5-palladium migration fol-lowed by the intramolecular arylation sequence. Because of the macrocyclic strain, the newly formed 9H-fuorene segment adopts curved structure, rendering highly rigid inherently chiral macrocycles unique chiroptical property.


inherent chirality
asymmetric synthesis
circularly polarized luminescence

Supplementary materials

Supporting information
supporting information containing experimental procedures and characterization data, copies of 1H and 13C NMR spectra.Photophysical and chiroptical prop-erties.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.