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Abstract Cyclophanes are a venerable class of macrocyclic and cage compounds that often contain unusual conformations, high strain, and unusual properties. However, synthesis of complex, functional derivatives remains difficult due to low functional group tolerance, high dilution, extreme reaction conditions, and sometimes low yields using traditional stepwise synthetic methods. “Design of experiments” (DOE) is a method employed for the optimization of reaction conditions, and we showcase this approach to generate a dramatic increase in the yield of specific targets from two different self‐assembling systems. These examples demonstrate that DOE provides an additional tool in tuning self‐assembling, dynamic covalent systems.
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Main Group Supramolecular Chemistry Led to Surprising New Directions in the Self-Assembly of Organic Macrocycles, Cages, and Cyclophanes
Abstract Cyclophanes are an admirable class of macrocyclic and cage compounds that often display unusual properties due to their high strain and unusual conformations. However, the exploration of new, complex cyclophanes has been encumbered by syntheses that can be low yielding, require harsh reaction conditions, and arduous purification steps. Herein, we discuss our work using metalloid-directed self-assembly and dynamic covalent chemistry to form cryptands. These were then subjected to mild conditions to produce discrete disulfide, thioether and hydrocarbon macrocycles in high yields. ‘Design of Experiments’ was then used to selectively synthesize targeted macrocycles from complex mixtures. 1 Introduction 2 Cryptands to Cyclophanes 3 Functionalizable Macrocycles 4 ‘Design of Experiments’ Targeted Synthesis 5 Conclusions and Outlook
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- PAR ID:
- 10309024
- Date Published:
- Journal Name:
- Synlett
- Volume:
- 32
- Issue:
- 17
- ISSN:
- 0936-5214
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1055/a-1389-9498
