Mechanochemical Route to Upper Rim Tetrafunctionalised Prochiral and Inherently Chiral Calix[4]arenes

Sean P. Bew; G. Richard Stephenson; Deeptee Horil Roy; William Gardiner; Luis Martinez Lozano

doi:10.26434/chemrxiv-2025-nzqg3

Mechanochemical Route to Upper Rim Tetrafunctionalised Prochiral and Inherently Chiral Calix[4]arenes

Sean P. Bew, G. Richard Stephenson, Deeptee Horil Roy, William Gardiner, Luis Martinez Lozano

Research output: Working paper › Preprint

Abstract

The application of an experimentally straightforward synthesis of upper rim tetrafunctionalised prochiral ABAB (AB ≠ H), ABBB (AB ≠ H), ABCB (ABC ≠ H) and inherently chiral, racemic calix[4]arenes (ABCD ≠ H) calix[4]arenes using a pestle and mortar as the ‘reaction flask'. These, till now, difficult-to-source modalities are generated via a combination of mechanochemistry, Cannizzaro and Suzuki-Miyaura or Sonogashira couplings which transform a simple to synthesise calix[4]arene starting material into structure and function diverse prochiral (i.e. ABCB) and racemic, inherently chiral ABCD cone-confined calix[4]arenes. Exploiting this methodology and filling an important ‘gap' in calix[4]arene chemistry, we report the first examples of ABCD calix[4]arenes appended with four different C-substituents (i.e. ABCD ≠ H) on the upper rim.

Original language	English
Publisher	ChemRxiv
DOIs	https://doi.org/10.26434/chemrxiv-2025-nzqg3
Publication status	Published - 9 Jul 2025

Keywords

calixarene
inherent chirality
mechanochemistry
transition metal catalysis
redox chemistry

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10.26434/chemrxiv-2025-nzqg3Licence: CC BY

Cite this

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abstract = "The application of an experimentally straightforward synthesis of upper rim tetrafunctionalised prochiral ABAB (AB ≠ H), ABBB (AB ≠ H), ABCB (ABC ≠ H) and inherently chiral, racemic calix[4]arenes (ABCD ≠ H) calix[4]arenes using a pestle and mortar as the {\textquoteleft}reaction flask'. These, till now, difficult-to-source modalities are generated via a combination of mechanochemistry, Cannizzaro and Suzuki-Miyaura or Sonogashira couplings which transform a simple to synthesise calix[4]arene starting material into structure and function diverse prochiral (i.e. ABCB) and racemic, inherently chiral ABCD cone-confined calix[4]arenes. Exploiting this methodology and filling an important {\textquoteleft}gap' in calix[4]arene chemistry, we report the first examples of ABCD calix[4]arenes appended with four different C-substituents (i.e. ABCD ≠ H) on the upper rim.",

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AU - Martinez Lozano, Luis

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