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Updated: Aug 11, 2025

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Inherently chiral calixarenes by a catalytic enantioselective desymmetrizing cross-dehydrogenative coupling
Xin Zhang1, Shuo Tong1, Jieping Zhu2
1Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University Beijing 100084 China tongshuo@mail.tsinghua.edu.cn http://mascl.group.
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.
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