This proposal intends to apply recent advances in the synthesis of new molecular scaffolds to several problems in molecular recognition. The new, cleft-shaped structures offer roomy interiors which can be functionalized along their concave linings with a variety of chemical surfaces. The functional groups converge to present acidic, basic and hydrophobic sites to smaller, convex shaped targets of interest. The availability of both lipophilic and hydrophilic derivatives will permit studies under a range of conditions. Specific problems to be addressed are the intermolecular forces of nitrogen-halogen interactions in solution, and the energetics of low barrier hydrogen bonds. In addition, the clefts will be used for asymmetric protonation and epoxidation reactions, the binding of metals in new ligand environments, and in combinatorial approaches to peptide recognition. By applying these methods to molecular recognition, it is hoped that introducing randomness to host design can give opportunities for the discovery of new, tight-binding complexes and molecular interactions that are unexpected or not well understood. By making these scaffolds known and accessible, it is expected that research in other areas of molecular recognition will be stimulated.

National Institute of Health (NIH)
National Institute of General Medical Sciences (NIGMS)
Method to Extend Research in Time (MERIT) Award (R37)
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Bio-Organic and Natural Products Chemistry Study Section (BNP)
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Scripps Research Institute
La Jolla
United States
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Ajami, Dariush; Rebek, Julius (2012) Reversibly expanded encapsulation complexes. Top Curr Chem 319:57-78
Lledo, Agusti; Kamioka, Seiji; Sather, Aaron C et al. (2011) Supramolecular architecture with a cavitand-capsule chimera. Angew Chem Int Ed Engl 50:1299-301
Berryman, Orion B; Dube, Henry; Rebek Jr, Julius (2011) Photophysics Applied to Cavitands and Capsules. Isr J Chem 51:700-709
Xiao, Shengxiong; Ajami, Dariush; Rebek Jr, Julius (2010) An extended cavitand with an introverted carboxylic acid. Chem Commun (Camb) 46:2459-61
Durola, Fabien; Rebek Jr, Julius (2010) The ouroborand: a cavitand with a coordination-driven switching device. Angew Chem Int Ed Engl 49:3189-91
Busseron, Eric; Rebek Jr, Julius (2010) Guest recognition in a partially bridged deep cavitand. Org Lett 12:4828-31
Lledó, Agustí; Restorp, Per; Rebek, Julius (2009) Pseudo-capsule assemblies characterized by 19F NMR techniques. J Am Chem Soc 131:2440-1
Pinacho Crisostomo, Fernando R; Lledo, Agusti; Shenoy, Siddhartha R et al. (2009) Recognition and organocatalysis with a synthetic cavitand receptor. J Am Chem Soc 131:7402-10
Xiao, Shengxiong; Ajami, Dariush; Rebek Jr, Julius (2009) Cavitands with mobile walls. Org Lett 11:3163-5
Purse, Byron W; Butterfield, Sara M; Ballester, Pablo et al. (2008) Interaction energies and dynamics of acid-base pairs isolated in cavitands. J Org Chem 73:6480-8

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