Zhang, XinTong, ShuoZhu, JiepingWang, Mei-Xiang2023-01-282023-01-282023-01-282023-01-2810.1039/D2SC06234Hhttps://infoscience.epfl.ch/handle/20.500.14299/194351Under the catalysis of PdBr2 and a chiral phosphoramidite ligand, the upper-rim mono (2-bromoaroyl)- substituted calix[4]arene derivatives underwent a facile enantioselective desymmetrization reaction to afford 9H-fluorene-embedded inherently chiral calixarenes in good yields with excellent enantioselectivities. The transannular dehydrogenative arene–arene coupling reaction proceeded most probably through an oxidative addition of the Caryl–Br bond to a ligated palladium catalyst followed by a sequence of an enantioselective 1,5-palladium migration and an intramolecular C–H arylation sequence. This new family of inherently chiral calixarenes possesses unique chiroptical properties thanks to their highly rigid structure induced by the 9H-fluorene segment.text::journal::journal article::research article