Pillar[5]arene as a co-factor in templating rotaxane formation.

After the manner in which coenzymes often participate in the binding of substrates in the active sites of enzymes, pillar[5]arene, a macrocycle containing five hydroquinone rings linked through their para positions by methylene bridges, modifies the binding properties of cucurbit[6]uril, such that the latter templates azide-alkyne cycloadditions that do not occur in the presence of only the cucurbit[6]uril, a macrocycle composed of six glycoluril residues doubly linked through their nitrogen atoms to each other by methylene groups. Here, we describe how a combination of pillar[5]arene and cucurbit[6]uril interacts cooperatively with bipyridinium dications substituted on their nitrogen atoms with 2-azidoethyl- to 5-azidopentyl moieties to afford, as a result of orthogonal templation, two [4]rotaxanes and one [5]rotaxane in >90% yields inside 2 h at 55 °C in acetonitrile. Since the hydroxyl groups on pillar[5]arene and the carbonyl groups on cucurbit[6]uril form hydrogen bonds readily, these two macrocycles work together in a cooperative fashion to the extent that the four conformational isomers of pillar[5]arene can be trapped on the dumbbell components of the [4]rotaxanes. In the case of the [5]rotaxane, it is possible to isolate a compound containing two pillar[5]arene rings with local C5 symmetries. In addition to fixing the stereochemistries of the pillar[5]arene rings, the regiochemistries associated with the 1,3-dipolar cycloadditions have been extended in their constitutional scope. Under mild conditions, orthogonal recognition motifs have been shown to lead to templation with positive cooperativity that is fast and all but quantitative, as well as being green and efficient.

[1]  Luke G Green,et al.  A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes. , 2002, Angewandte Chemie.

[2]  M. Tamura,et al.  Diels-Alder in Aqueous Molecular Hosts: Unusual Regioselectivity and Efficient Catalysis , 2006, Science.

[3]  Yoshihisa Inoue,et al.  Complexation Thermodynamics of Cucurbit[6]uril with Aliphatic Alcohols, Amines, and Diamines , 2007 .

[4]  D. Tuncel,et al.  Supramolecular Assemblies Constructed by Cucurbituril‐Catalyzed Click Reaction , 2011 .

[5]  Yoshiaki Nakamoto,et al.  para-Bridged symmetrical pillar[5]arenes: their Lewis acid catalyzed synthesis and host-guest property. , 2008, Journal of the American Chemical Society.

[6]  Jishan Wu,et al.  Efficient preparation of separable pseudo[n]rotaxanes by selective threading of oligoalkylammonium salts with cucurbit[7]uril. , 2009, Chemistry.

[7]  T. Ogoshi,et al.  Reversibly tunable lower critical solution temperature utilizing host-guest complexation of pillar[5]arene with triethylene oxide substituents. , 2012, Journal of the American Chemical Society.

[8]  U. Kortz,et al.  Dynamically self-assembling metalloenzyme models based on calixarenes. , 2006, Angewandte Chemie.

[9]  Shunya Tanaka,et al.  Ionic Liquid Molecules (ILs) as Novel Guests for Pillar[5]arene: 1:2 Host–Guest Complexes between Pillar[5]arene and ILs in Organic Media , 2011 .

[10]  Y. Ko,et al.  Highly stereoselective photocyclodimerization of alpha-cyclodextrin-appended anthracene mediated by gamma-cyclodextrin and cucurbit[8]uril: a dramatic steric effect operating outside the binding site. , 2008, Journal of the American Chemical Society.

[11]  G. Ercolani,et al.  Allosteric, chelate, and interannular cooperativity: a mise au point. , 2011, Angewandte Chemie.

[12]  B. Breit,et al.  Self-assembled bidentate ligands for Ru-catalyzed anti-Markovnikov hydration of terminal alkynes. , 2006, Angewandte Chemie.

[13]  W. Nau,et al.  Transition-metal-promoted chemoselective photoreactions at the cucurbituril rim. , 2011, Angewandte Chemie.

[14]  A. Wego,et al.  Complex Formation between Cucurbit[n]urils and Alkali, Alkaline Earth and Ammonium Ions in Aqueous Solution , 2001 .

[15]  Y. Ko,et al.  Complexation of aliphatic ammonium ions with a water-soluble cucurbit[6]uril derivative in pure water: isothermal calorimetric, NMR, and X-ray crystallographic study. , 2009, Chemistry.

[16]  M. Komiyama,et al.  Trinuclear copper(II) complex showing high selectivity for the hydrolysis of 2'-5' over 3'-5' for UpU and 3'-5' over 2'-5' for ApA ribonucleotides. , 2002, Journal of the American Chemical Society.

[17]  Yu Liu,et al.  Dual supramolecular photochirogenesis: ultimate stereocontrol of photocyclodimerization by a chiral scaffold and confining host. , 2011, Journal of the American Chemical Society.

[18]  Xiaoyong Lu,et al.  Silver-promoted desilylation catalyzed by ortho- and allosteric cucurbiturils. , 2010, Organic letters.

[19]  Lyle Isaacs,et al.  The cucurbit[n]uril family. , 2005, Angewandte Chemie.

[20]  R. Iizuka,et al.  Cyclic host liquids for facile and high-yield synthesis of [2]rotaxanes. , 2012, Journal of the American Chemical Society.

[21]  J. Rebek,et al.  Expanded capsules with reversibly added spacers. , 2006, Journal of the American Chemical Society.

[22]  J. Steinke,et al.  Mainchain pseudopolyrotaxanes viapost-threading with cucurbituril , 2001 .

[23]  Yu Liu,et al.  Catalytic enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid mediated by a non-sensitizing chiral metallosupramolecular host. , 2009, Angewandte Chemie.

[24]  Günter Szeimies,et al.  1.3-Dipolare Cycloadditionen, XXXII. Kinetik der Additionen organischer Azide an CC-Mehrfachbindungen , 1967 .

[25]  S. Fujinami,et al.  Synthesis and conformational characteristics of alkyl-substituted pillar[5]arenes. , 2010, The Journal of organic chemistry.

[26]  D. Tuncel,et al.  pH-Triggered dethreading-rethreading and switching of cucurbit[6]uril on bistable [3]pseudorotaxanes and [3]rotaxanes. , 2008, Chemistry.

[27]  Q. Luo,et al.  Artificial enzymes based on supramolecular scaffolds. , 2012, Chemical Society reviews.

[28]  S. Fujinami,et al.  Facile, rapid, and high-yield synthesis of pillar[5]arene from commercially available reagents and its X-ray crystal structure. , 2011, The Journal of organic chemistry.

[29]  J. Rebek,et al.  Acceleration of a Diels–Alder reaction by a self-assembled molecular capsule , 1997, Nature.

[30]  J. F. Stoddart,et al.  Cooperative self-assembly: producing synthetic polymers with precise and concise primary structures. , 2012, Chemical Society reviews.

[31]  David J. Williams,et al.  Anion‐Assisted Self‐Assembly , 1997 .

[32]  David J. Williams,et al.  Host-Guest Chemistry Aids and Abets a Stereospecific Photodimerization in the Solid State. , 2001, Angewandte Chemie.

[33]  T. Ogoshi,et al.  Planar-chiral pillar[5]arene: chiral switches induced by multiexternal stimulus of temperature, solvents, and addition of achiral guest molecule. , 2011, The Journal of organic chemistry.

[34]  E. Anslyn,et al.  Proton inventory of a bifunctional ribonuclease model , 1989 .

[35]  Cheng Yang,et al.  Pressure and temperature-controlled enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate mediated by secondary face- and skeleton-modified γ-cyclodextrins , 2006 .

[36]  J. F. Stoddart,et al.  Template-directed syntheses of rigid oligorotaxanes under thermodynamic control. , 2010, Angewandte Chemie.

[37]  Michael D. Pluth,et al.  Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis , 2007, Science.

[38]  Arieh Warshel,et al.  Dynamical contributions to enzyme catalysis: critical tests of a popular hypothesis. , 2006, Chemical reviews.

[39]  Harry L Anderson,et al.  What is cooperativity? , 2009, Angewandte Chemie.

[40]  J. Steinke,et al.  Catalytic Self-Threading: A New Route for the Synthesis of Polyrotaxanes , 2004 .

[41]  M. Fujita,et al.  Coordination assemblies from a Pd(II)-cornered square complex. , 2005, Accounts of chemical research.

[42]  O. Scherman,et al.  Sequence-specific self-sorting of the binding sites of a ditopic guest by cucurbituril homologues and subsequent formation of a hetero[4]pseudorotaxane. , 2009, Chemistry.

[43]  Hao Li,et al.  Quantitative emergence of hetero[4]rotaxanes by template-directed click chemistry. , 2013, Angewandte Chemie.

[44]  W. L. Mock,et al.  Cycloaddition induced by cucurbituril. A case of Pauling principle catalysis , 1983 .

[45]  Michael K. Gilson,et al.  Erratum: “Grid inhomogeneous solvation theory: Hydration structure and thermodynamics of the miniature receptor cucurbit[7]uril” [J. Chem. Phys. 137, 044101 (2012)] , 2012 .

[46]  C. Hunter,et al.  Quantifying intermolecular interactions: guidelines for the molecular recognition toolbox. , 2004, Angewandte Chemie.

[47]  Lingyun Wang,et al.  A facile and efficient preparation of pillararenes and a pillarquinone. , 2009, Angewandte Chemie.

[48]  Barry B Snushall,et al.  Controlling factors in the synthesis of cucurbituril and its homologues. , 2001, The Journal of organic chemistry.

[49]  T. Ogoshi,et al.  Photoreversible transformation between seconds and hours time-scales: threading of pillar[5]arene onto the azobenzene-end of a viologen derivative. , 2011, The Journal of organic chemistry.

[50]  T. Ogoshi,et al.  High Yield Synthesis of Polyrotaxane Constructed from Pillar[5]arene and Viologen Polymer and Stabilization of Its Radical Cation , 2010 .

[51]  T. Ogoshi,et al.  Planar-chiral macrocyclic host pillar[5]arene: no rotation of units and isolation of enantiomers by introducing bulky substituents. , 2011, Organic letters.

[52]  Christopher M. Andolina,et al.  Tethered dinuclear europium(III) macrocyclic catalysts for the cleavage of RNA. , 2008, Journal of the American Chemical Society.

[53]  张明明,et al.  1,4-双正丙氧基柱[7]芳烃的合成及主客体化学 , 2012 .

[54]  J. F. Stoddart,et al.  pH-responsive supramolecular nanovalves based on cucurbit[6]uril pseudorotaxanes. , 2008, Angewandte Chemie.

[55]  Zhan-Ting Li,et al.  Pillar[n]arenes (n = 8-10) with two cavities: synthesis, structures and complexing properties. , 2012, Chemical communications.

[56]  B. Salih,et al.  Molecular switch based on a cucurbit[6]uril containing bistable [3]rotaxane. , 2007, Chemical communications.

[57]  J. F. Stoddart,et al.  Mechanical bond-induced radical stabilization. , 2013, Journal of the American Chemical Society.

[58]  Y. Ko,et al.  A facile, stereoselective [2 + 2] photoreaction mediated by curcurbit[8]uril. , 2001, Chemical communications.

[59]  J. F. Stoddart,et al.  Monofunctionalized pillar[5]arene as a host for alkanediamines. , 2011, Journal of the American Chemical Society.

[60]  Douglas C. Friedman,et al.  Positive cooperativity in the template-directed synthesis of monodisperse macromolecules. , 2012, Journal of the American Chemical Society.

[61]  Morten Meldal,et al.  Peptidotriazoles on solid phase: [1,2,3]-triazoles by regiospecific copper(i)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides. , 2002, The Journal of organic chemistry.

[62]  Takumi Yamaguchi,et al.  Asymmetric [2 + 2] olefin cross photoaddition in a self-assembled host with remote chiral auxiliaries. , 2008, Journal of the American Chemical Society.

[63]  W. L. Mock,et al.  Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation , 1989 .

[64]  Takumi Yamaguchi,et al.  Unusual [2+4] and [2+2] cycloadditions of arenes in the confined cavity of self-assembled cages. , 2007, Journal of the American Chemical Society.

[65]  F. Maseras,et al.  A theoretical analysis of a classic example of supramolecular catalysis. , 2007, Chemical communications.

[66]  Oren A Scherman,et al.  Release of high-energy water as an essential driving force for the high-affinity binding of cucurbit[n]urils. , 2012, Journal of the American Chemical Society.

[67]  Kevin D. Haenni,et al.  The application of CuAAC 'click' chemistry to catenane and rotaxane synthesis. , 2010, Chemical Society reviews.

[68]  Adrian Whitty,et al.  Cooperativity and biological complexity. , 2008, Nature chemical biology.

[69]  A. J. Kirby,et al.  Enzyme Mechanisms, Models, and Mimics , 1996 .

[70]  R. Huisgen Kinetics and reaction mechanisms: selected examples from the experience of forty years , 1989 .

[71]  Ronald Breslow,et al.  Biomimetic Chemistry and Artificial Enzymes: Catalysis by Design , 1995 .

[72]  B. Salih,et al.  pH-Responsive polypseudorotaxane synthesized through cucurbit[6]uril catalyzed 1,3-dipolar cycloaddition , 2006 .

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

[74]  B. Breit,et al.  Self-assembly of bidentate ligands for combinatorial homogeneous catalysis: methanol-stable platforms analogous to the adenine-thymine base pair. , 2007, Angewandte Chemie.

[75]  J. Steinke,et al.  The synthesis of [2], [3] and [4]rotaxanes and semirotaxanes. , 2002, Chemical communications.

[76]  D. Fiedler,et al.  Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels. , 2004, Accounts of chemical research.

[77]  E. Kelderman,et al.  Supramolecular Catalysis of Ester and Amide Cleavage by a Dinuclear Barium(II) Complex. , 1999, Angewandte Chemie.

[78]  J. F. Stoddart,et al.  A self-complexing and self-assembling pillar[5]arene. , 2012, Chemical communications.

[79]  Arieh Warshel,et al.  Energetics and Dynamics of Enzymatic Reactions , 2001 .

[80]  Jae Wook Lee,et al.  Cucurbituril homologues and derivatives: new opportunities in supramolecular chemistry. , 2003, Accounts of chemical research.

[81]  Masao Kawai,et al.  Sequential formation of a ternary complex among dihexylammonium, cucurbit[6]uril, and cyclodextrin with positive cooperativity. , 2006, Organic letters.

[82]  J. Rebek,et al.  Self-Assembled Capsules of Unprecedented Shapes , 2011, Angewandte Chemie.

[83]  J. Mague,et al.  Template directed photodimerization of trans-1,2-bis(n-pyridyl)ethylenes and stilbazoles in water. , 2005, Chemical communications.

[84]  Ruibing Wang,et al.  Cucurbit[7]uril mediates the stereoselective [4+4] photodimerization of 2-aminopyridine hydrochloride in aqueous solution. , 2006, The Journal of organic chemistry.

[85]  Chunju Li,et al.  Complex interactions of pillar[5]arene with paraquats and bis(pyridinium) derivatives. , 2010, Organic & biomolecular chemistry.

[86]  Andrea Sartori,et al.  Catalysis of diribonucleoside monophosphate cleavage by water soluble copper(II) complexes of calix[4]arene based nitrogen ligands. , 2006, Journal of the American Chemical Society.

[87]  H. Meier,et al.  Synthesis of pillar[7]arene , 2012 .

[88]  J. Steinke,et al.  Catalytically self-threading polyrotaxanes , 1999 .

[89]  Mikael P. Backlund,et al.  Enzyme-like control of carbocation deprotonation regioselectivity in supramolecular catalysis of the Nazarov cyclization. , 2011, Angewandte Chemie.

[90]  J. F. Stoddart,et al.  Incorporation of an A1/A2-difunctionalized pillar[5]arene into a metal-organic framework. , 2012, Journal of the American Chemical Society.

[91]  Cheng Yang,et al.  Supramolecular enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate mediated by capped gamma-cyclodextrins: critical control of enantioselectivity by cap rigidity. , 2008, The Journal of organic chemistry.

[92]  M. G. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001, Angewandte Chemie.

[93]  Eric Masson,et al.  Cucurbituril chemistry: a tale of supramolecular success , 2012 .

[94]  Z Jane Wang,et al.  A supramolecular approach to combining enzymatic and transition metal catalysis , 2013, Nature Chemistry.

[95]  T. Ogoshi,et al.  Effect of an Intramolecular Hydrogen Bond Belt and Complexation with the Guest on the Rotation Behavior of Phenolic Units in Pillar[5]arenes , 2010 .

[96]  Jishan Wu,et al.  Efficient synthesis of a hetero[4]rotaxane by a "threading-stoppering-followed-by-clipping" approach. , 2010, Organic & biomolecular chemistry.

[97]  T. Ogoshi,et al.  Synthesis and conformational characteristics of nonsymmetric pillar[5]arene. , 2010, Organic letters.

[98]  Lyle Isaacs,et al.  The cucurbit[n]uril family: prime components for self-sorting systems. , 2005, Journal of the American Chemical Society.