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Inherently chiral calixarenes by a catalytic enantioselective desymmetrizing cross-dehydrogenative coupling† † Electronic supplementary information (ESI) available. CCDC 2216266 and 2216267. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d2sc06234h

ABSTRACT: Under 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. Reported here is the catalytic enantioselective desymmetrization of calixarene skeletons for the construction of inherently chiral calixarenes through a transannular arene–arene dehydrogenative coupling reaction.

SUBMITTER: Zhang X

PROVIDER: S-EPMC9890570 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

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