Synthesis of Water-Soluble Deep-Cavity Cavitands.

An efficient, four-step synthesis of a range of water-soluble, deep-cavity cavitands is presented. Key to this approach are octahalide derivatives (4, X = Cl or Br) that allow a range of water-solubilizing groups to be added to the outer surface of the core host structure. In many cases, the conversion of the starting dodecol (1) resorcinarene to the different cavitands avoids any chromatographic procedures.

[1]  Scott M. Grayson,et al.  A versatile and modular approach to functionalisation of deep-cavity cavitands via"click" chemistry. , 2011, Chemical communications.

[2]  B. Gibb,et al.  Molecular containers assembled through the hydrophobic effect. , 2015, Chemical Society reviews.

[3]  S. Jockusch,et al.  Controlling photoreactions with restricted spaces and weak intermolecular forces: exquisite selectivity during oxidation of olefins by singlet oxygen. , 2007, Journal of the American Chemical Society.

[4]  B. Gibb,et al.  Templated assembly of water-soluble nano-capsules: inter-phase sequestration, storage, and separation of hydrocarbon gases. , 2006, Journal of the American Chemical Society.

[5]  Corinne L. D. Gibb,et al.  Binding of cyclic carboxylates to octa-acid deep-cavity cavitand , 2014, Journal of Computer-Aided Molecular Design.

[6]  B. Gibb,et al.  Anion binding to hydrophobic concavity is central to the salting-in effects of Hofmeister chaotropes. , 2011, Journal of the American Chemical Society.

[7]  Zhan-Ting Li,et al.  Supramolecular organic frameworks: engineering periodicity in water through host-guest chemistry. , 2016, Chemical communications.

[8]  Lyle Isaacs,et al.  Acyclic cucurbit[n]uril molecular containers enhance the solubility and bioactivity of poorly soluble pharmaceuticals , 2012, Nature Chemistry.

[9]  Adam R. Urbach,et al.  Sequence-specific, nanomolar peptide binding via cucurbit[8]uril-induced folding and inclusion of neighboring side chains. , 2015, Journal of the American Chemical Society.

[10]  B. Gibb,et al.  Chiral Photochemistry in a Confined Space: Torquoselective Photoelectrocyclization of Pyridones within an Achiral Hydrophobic Capsule. , 2009, Tetrahedron.

[11]  B. Gibb,et al.  Templation of the excited-state chemistry of alpha-(n-alkyl) dibenzyl ketones: how guest packing within a nanoscale supramolecular capsule influences photochemistry. , 2008, Journal of the American Chemical Society.

[12]  A. Kaifer,et al.  Encapsulation of ferrocene and peripheral electrostatic attachment of viologens to dimeric molecular capsules formed by an octaacid, deep-cavity cavitand. , 2008, Chemistry.

[13]  V. Ramamurthy,et al.  Supramolecular photochemistry: from molecular crystals to water-soluble capsules. , 2015, Chemical Society reviews.

[14]  Severin T. Schneebeli,et al.  Functionalizing pillar[n]arenes. , 2014, Accounts of chemical research.

[15]  V. Ramamurthy,et al.  New water-soluble organic capsules are effective in controlling excited-state processes of guest molecules. , 2011, Organic letters.

[16]  F. Raymo,et al.  Reversible Disassembly-Assembly of Octa Acid-Guest Capsule in Water Triggered by a Photochromic Process. , 2016, Organic letters.

[17]  Punidha Sokkalingam,et al.  Binding Hydrated Anions with Hydrophobic Pockets. , 2016, Journal of the American Chemical Society.

[18]  S. Rick,et al.  Kinetic resolution of constitutional isomers controlled by selective protection inside a supramolecular nanocapsule. , 2010, Nature chemistry.

[19]  B. Gibb,et al.  Anion complexation and the Hofmeister effect. , 2014, Angewandte Chemie.

[20]  Yong Yang,et al.  Pillararenes, a new class of macrocycles for supramolecular chemistry. , 2012, Accounts of chemical research.

[21]  Simin Liu,et al.  An improved synthesis of ‘octa-acid’ deep-cavity cavitand , 2011, Supramolecular chemistry.

[22]  A. Kaifer,et al.  Encapsulation of tetrathiafulvalene inside a dimeric molecular capsule. , 2011, Organic letters.

[23]  B. Gibb,et al.  C-H...X--R (X = Cl, Br, and I) hydrogen bonds drive the complexation properties of a nanoscale molecular basket. , 2001, Journal of the American Chemical Society.

[24]  A. Kaifer,et al.  Trapping of bulky guests inside dimeric molecular capsules formed by a deep-cavity cavitand. , 2012, The Journal of organic chemistry.

[25]  L. Isaacs,et al.  Uptake of Hydrocarbons in Aqueous Solution by Encapsulation in Acyclic Cucurbit[n]uril-Type Molecular Containers. , 2016, Angewandte Chemie.

[26]  B. Gibb,et al.  Controlling photochemistry with distinct hydrophobic nanoenvironments. , 2004, Journal of the American Chemical Society.