Inherently chiral calixarenes by a catalytic enantioselective desymmetrizing cross-dehydrogenative coupling

Xin Zhang; Shuo Tong; Jieping Zhu; Mei-Xiang Wang

doi:10.1039/D2SC06234H

Inherently chiral calixarenes by a catalytic enantioselective desymmetrizing cross-dehydrogenative coupling†

Xin Zhang,^a Shuo Tong,

*^a Jieping Zhu

^b and Mei-Xiang Wang

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* Corresponding authors

^a Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China
E-mail: tongshuo@mail.tsinghua.edu.cn
Web: http://mascl.group

^b Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne, Switzerland

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 C_aryl–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.

This article is part of the themed collections: Most popular 2023 polymer and supramolecular chemistry articles, 2023 Chemical Science HOT Article Collection and 2023 ChemSci Pick of the Week Collection

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DOI: https://doi.org/10.1039/D2SC06234H
Article type: Edge Article
Submitted: 11 Nov 2022
Accepted: 05 Dec 2022
First published: 06 Dec 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2023,14, 827-832

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Inherently chiral calixarenes by a catalytic enantioselective desymmetrizing cross-dehydrogenative coupling

X. Zhang, S. Tong, J. Zhu and M. Wang, Chem. Sci., 2023, 14, 827 DOI: 10.1039/D2SC06234H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Chemical Science

Inherently chiral calixarenes by a catalytic enantioselective desymmetrizing cross-dehydrogenative coupling†

Abstract

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Inherently chiral calixarenes by a catalytic enantioselective desymmetrizing cross-dehydrogenative coupling

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