Developing An Entirely Mechanochemical Synthesis of Cram’s Cavitands and Carcerands
- 1School of Chemistry, University of Birmingham, Edgbaston, Birmingham, United Kingdom, B152TT
- 2Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, Canada, H3A0B8
Abstract
We report the development of an entirely mechanochemical synthesis of a set of iconic and complex supramolecular targets, Cram’s carcerands and cavitands, using a sequence of mechanochemical, liquid-assisted steps. By demonstrating how mechanochemical methods can be adapted to each segment of carcerand synthesis, this work highlights the benefits and opportunities mechanochemistry offers for simpler, high-yielding synthesis of complex targets. This work exploits grinding based on dual asymmetric centrifugal motion, which provides high autogenous frictional heating to drive chemical reactivity and, in some cases, permits thick and resinous reaction systems to mix without solidifying. The analogous media-free approach provided efficient mixing when heating was not required. Using these methods, we show that a set of phenolic cavitands, which are crucial precursors to a wide set of carcerands and hemicarcerands, can be synthesized rapidly, in high yields, using minimal organic solvent, and with improved operational simplicity, and that the final capsule-like carcerands can also be assembled mechanochemically, despite the common expectation that effectiveness of such supramolecular transformations requires high dilutions.
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BibTeX
@misc{marrett2026developing,
title = {{Developing An Entirely Mechanochemical Synthesis of Cram’s Cavitands and Carcerands}},
author = {Joseph M. Marrett and Hatem M. Titi and Tomislav Friscic},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009991/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009991/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Developing An Entirely Mechanochemical Synthesis of Cram’s Cavitands and Carcerands
AU - Joseph M. Marrett
AU - Hatem M. Titi
AU - Tomislav Friscic
PY - 2026
DA - 2026/10/06
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009991/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009991/v1
AB - We report the development of an entirely mechanochemical synthesis of a set of iconic and complex supramolecular targets, Cram’s carcerands and cavitands, using a sequence of mechanochemical, liquid-assisted steps. By demonstrating how mechanochemical methods can be adapted to each segment of carcerand synthesis, this work highlights the benefits and opportunities mechanochemistry offers for simpler, high-yielding synthesis of complex targets. This work exploits grinding based on dual asymmetric centrifugal motion, which provides high autogenous frictional heating to drive chemical reactivity and, in some cases, permits thick and resinous reaction systems to mix without solidifying. The analogous media-free approach provided efficient mixing when heating was not required. Using these methods, we show that a set of phenolic cavitands, which are crucial precursors to a wide set of carcerands and hemicarcerands, can be synthesized rapidly, in high yields, using minimal organic solvent, and with improved operational simplicity, and that the final capsule-like carcerands can also be assembled mechanochemically, despite the common expectation that effectiveness of such supramolecular transformations requires high dilutions.
ER -