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Published on: September 18, 2016
A bis-calixarene from olefin metathesis
Shimelis T Hailu1, Ray J Butcher, Paul F Hudrlik
1Department of Chemistry, Howard University, 525 College Street, NW, Washington, DC 2059, USA.
Summary
A novel bis-calixarene cage was synthesized using ring-closing olefin metathesis. This macrocycle features two calix[4]arene units linked by butenyl groups, forming a unique cage structure with specific conformational properties.
Area of Science:
- Supramolecular Chemistry
- Organic Synthesis
- Materials Science
Background:
- Calixarenes are versatile macrocyclic compounds with a wide range of applications.
- Developing novel macrocyclic structures with defined conformations is crucial for host-guest chemistry and materials science.
- Olefin metathesis is a powerful tool for constructing carbon-carbon double bonds and complex molecular architectures.
Purpose of the Study:
- To synthesize a novel bis-calixarene macrocycle using ring-closing olefin metathesis.
- To characterize the structure and conformation of the synthesized bis-calixarene.
- To investigate the potential of this new macrocycle in host-guest chemistry or materials applications.
Main Methods:
- Synthesis of tetra-kis-(allyl-oxy)calix[4]arene precursor.
- Ring-closing olefin metathesis reaction using a suitable catalyst.
- Purification and characterization of the resulting bis-calixarene by NMR spectroscopy and X-ray crystallography.
Main Results:
- Successful synthesis of a bis-calixarene cage molecule with the chemical formula C(74)H(68)O(8).
- X-ray crystallography revealed a flattened cone conformation for each calix[4]arene unit, with specific dihedral angles between aryl groups.
- No guest molecules were observed within the cage, and disorder was noted in the alkene carbons of one linker.
Conclusions:
- The study demonstrates the feasibility of constructing complex bis-calixarene macrocycles via olefin metathesis.
- The unique conformational features of the synthesized cage may offer opportunities for selective molecular recognition.
- Further studies are warranted to explore the host-guest properties and potential applications of this novel macrocyclic structure.
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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Overview
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Epoxidation with Peroxy Acids
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