Journal article
Programming Rapid Functional Group Diversification into a Solid‐State Reaction: Aryl Nitriles for Self‐Assembly, Click Reactivity, and Discovery of Coexisting Supramolecular Synthons
Chemistry : a European journal, Vol.28(37), p.e202200978
07/01/2022
DOI: 10.1002/chem.202200978
PMID: 35507693
Abstract
A method to rapidly diversify the molecules formed in organic crystals is introduced, with aryl nitriles playing a novel dual role as both hydrogen‐bond acceptors and modifiable organic groups. The discovery of coexisting supramolecular synthons in the same crystal is also described. The general concept is demonstrated by using a bis(aryl nitrile) alkene that undergoes a hydrogen‐bond‐directed intermolecular [2+2] photodimerization to form a tetra(aryl nitrile)cyclobutane. The product is readily converted by click reactivity to a tetra(aryl tetrazole) and by hydrolysis to a tetra(aryl carboxylic acid). The integration of aryl nitriles into solid‐state reactions opens broad avenues to post‐modify products formed in crystalline solids for rapid diversification.
Getting a handle on diversification: Aryl nitriles have been used to support hydrogen‐bond‐driven self‐assembly in the solid state to achieve an intermolecular photodimerization. The resulting tetrafunctionalized cyclobutane is amenable to rapid diversification as demonstrated by a post‐click modification. The integration of aryl nitriles as supramolecular handles allows the self‐assembly process to be programmed for post‐modification and conversion of the product to a wide variety of molecules.
Details
- Title: Subtitle
- Programming Rapid Functional Group Diversification into a Solid‐State Reaction: Aryl Nitriles for Self‐Assembly, Click Reactivity, and Discovery of Coexisting Supramolecular Synthons
- Creators
- Changan Li - University of IowaDale C. Swenson - University of Iowa, ChemistryLeonard R. MacGillivray - University of Iowa, Chemistry
- Resource Type
- Journal article
- Publication Details
- Chemistry : a European journal, Vol.28(37), p.e202200978
- DOI
- 10.1002/chem.202200978
- PMID
- 35507693
- ISSN
- 0947-6539
- eISSN
- 1521-3765
- Number of pages
- 6
- Grant note
- National Science Foundation (DMR-1708673; CHE-1828117)
- Language
- English
- Date published
- 07/01/2022
- Academic Unit
- Pharmaceutical Sciences and Experimental Therapeutics; Chemistry
- Record Identifier
- 9984276460102771
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