Assembly of Water‐Soluble,Dynamic, Covalent Container Molecules and Their Application in the Room‐Temperature Stabilization of Protoadamantene |
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Authors: | Dr. Zhihua Lin Junling Sun Bisera Efremovska Dr. Ralf Warmuth |
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Affiliation: | Department of Chemistry & Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, NJ 08854 (USA), Fax: (+1)?732 445 5312 |
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Abstract: | The thermodynamically controlled reactions of water‐soluble tetraformylcavitand 2 with two equivalents of H2N(CH2)nNH2 (n=2–4) in the presence of a suitable templating guest give hemicarceplexes 1 a – c? guest, the yield of which depends on the match between size and shape of the guest and that of the inner phase. These hemicarceplexes are dynamic and dissociate upon addition of acid and reform upon basification. In water, they exchange guests through temporary hydrolysis of imine bonds. To test 1 b as molecular reaction flask, 3‐noradamantyldiazirine 6 was encapsulated and photolyzed at 350 nm to produce Bredt olefin protoadamantene 5 and 1‐noradamantyldiazomethane 8 in a 4:1 ratio. Encapsulated protoadamantene is stable for days at room temperature in (CD3)2SO/CD3CN (t1/2=5.5 days) and has a lifetime of several minutes in D2O. |
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Keywords: | Bredt olefins dynamic covalent chemistry host– guest chemistry molecular container compound reactive intermediates |
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