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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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Expanding the Scope of Pnictogen‐Assisted Cyclophane Self‐Assembly
Abstract Cyclophanes are a fundamentally interesting class of compounds that host a wide range of unique and emergent properties. However, synthesis of complex and/or functionalized cyclophanes can often suffer from harsh reaction conditions, long reaction times, and sometimes low yields using stepwise methods. We have previously reported an efficient, high‐yielding, metalloid‐directed self‐assembly method to prepare disulfide, thioether, and hydrocarbon cyclophanes and cages that feature mercaptomethyl‐arenes as starting materials. Herein, we report the synthesis of 21 new disulfide and thioether assemblies that expand this high yielding self‐assembly method to a wide breadth of macrocycles and cages with diverse structures. Remarkably, the high‐yielding, efficient syntheses still proceed under dynamic covalent control using electron‐deficient, heteroaryl, cycloalkyl, spiro, and even short alkenyl/alkynyl substrates.
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- PAR ID:
- 10368882
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- European Journal of Organic Chemistry
- Volume:
- 2022
- Issue:
- 26
- ISSN:
- 1434-193X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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