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Updated: Jun 30, 2026
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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Sulfimidation of thioether groups--a versatile method for modifying and linking thia/oxa crowns
Mark R J Elsegood1, Paul F Kelly, Gillian Reid
1Department of Chemistry, Loughborough University, Loughborough, UK LE11 3TU.
Dalton Transactions (Cambridge, England : 2003)
|September 20, 2008
Summary
New sulfimidated crown ethers were synthesized by reacting thioether/ether crowns with o-mesitylsulfonylhydroxylamine (MSH). These novel compounds, including bicyclic structures, were characterized, expanding the scope of sulfur-nitrogen chemistry in macrocyclic systems.
Area of Science:
- Macrocyclic Chemistry
- Sulfur-Nitrogen Chemistry
- Organic Synthesis
Background:
- Crown ethers are versatile macrocyclic ligands with diverse applications.
- Functionalization of crown ethers with sulfur and nitrogen atoms offers unique chemical properties.
- Sulfimide chemistry provides a pathway to novel N-bridged structures.
Purpose of the Study:
- To synthesize and characterize novel sulfimidated crown ether derivatives.
- To explore the formation of mono- and di-sulfimidated species from mixed thioether/ether crowns.
- To investigate the synthesis of N-bridged bicyclic sulfimide compounds.
Main Methods:
- Reaction of mixed thioether/ether crown ethers ([9]aneO2S, [12]aneO3S, [18]aneO4S2) with o-mesitylsulfonylhydroxylamine (MSH).
- Deprotonation with lithium diisopropylamide (LDA) followed by reaction with N-bromosuccinimide (NBS) to form N-bridged structures.
- Isolation and purification of products as mesitylsulfonate ([mesSO3]-) and tetraphenylborate ([BPh4]-) salts.
- Characterization using X-ray crystallography and spectroscopic methods (NMR, IR).
Main Results:
- Successful synthesis of mono- and di-sulfimidated crown ethers, {[9]aneO2(S=NH2)}+, {[12]aneO3(S=NH2)}+, {[18]aneO4S(S=NH2)}+, and {[18]aneO4(S=NH2)2}2+.
- Formation of N-bridged bicyclic sulfimide compounds through LDA/NBS treatment.
- Synthesis of a unique cation, {([18]aneO4S2)N}+, featuring an intramolecular S-N-S bridge.
- Crystallographic and spectroscopic data confirm the structures of the synthesized compounds.
Conclusions:
- The study demonstrates a facile route to novel sulfimidated crown ethers and N-bridged bicyclic systems.
- The reactivity of mixed thioether/ether crowns with aminating agents is effectively showcased.
- The synthesized compounds represent new structural motifs in macrocyclic chemistry with potential for further exploration.
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