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CC BY 4.0 · Synlett 2025; 36(03): 216-225
DOI: 10.1055/s-0043-1775380
DOI: 10.1055/s-0043-1775380
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Ketocalixarenes: Versatile yet still Unexplored Macrocycles
This work was supported by the Israel Science Foundation (ISF), Grant No. 262/20.
This paper is dedicated to the memory of our collaborator and friend Dr. Norbert Itzhak
Abstract
Ketocalix[n]arenes can be prepared via oxidation of the methylene groups of protected calix[n]arenes. The presence of carbonyl groups at the bridges alters the preferred conformation and reactivity of the macrocycle and provides an entry point (via nucleophilic additions reactions) to a wide array of methylene-substituted derivatives as well as calix[n]radialenes.
1 Introduction
2 Synthesis of Ketocalix[n]arenes
2.1 Ketocalix[4]arene Derivatives
2.2 Systems Possessing both Carbonyl and Bromomethane Bridges
2.3 Pentaoxoketocalix[5]arene and Hexaoxoketocalix[6]arene Derivatives
2.4 Monooxo- and Dioxoketocalix[6]arenes
3 Conformation of Ketocalixarenes
4 Reactions of Ketocalixarenes
4.1 Alkylation of the OH Groups
4.2 Intramolecular Aromatic Nucleophilic Substitution
4.3 Reduction of the Carbonyl Groups
4.4 Reaction of 5c with PhLi
4.5 Reaction with tert-Butyllithium
5 From Ketocalix[n]arenes to Calix[n]radialenes and Calix[n]rotanes
6 Summary and Outlook
Publication History
Received: 22 May 2024
Accepted after revision: 10 June 2024
Article published online:
12 August 2024
© 2024. This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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For reviews on calixarenes, see:
For a review on the intramolecular hydrogen bonding in calixarenes, see:
For reviews on calixarenes modified at the methylene bridges, see:
For a recent study on spirodienone derivatives of 2,14, dithiacalix[4]arene, see
A similar conformation was also observed in thiacalixarenes with bridges oxidized to sulfonyl groups:
For a review, see