halogen‐bonded (a) capsule and (b) c...Figure 4.17 [Bis(pyridine)iodine(I)]+ tetrafluoroborate can be used as ...Figure 4.18 (a) Cyclization reaction of carbonyl groups with alkynes. The r...Figure 4.19 The proposed mechanism of cyclobromination of 4‐penten‐1‐ol ind...Figure 4.20 Reactions of alkenes with halonium ions that are stabilized by ...Figure 4.21 Plausible mechanism for the oxidation reactions of alcohols, as ...Figure 4.22 The mechanism of bromolactonization of unsaturated carboxylic a...Figure 4.23 Structures of (a) (DHQD)2PHAL and DCDMH [60] and (b) the catalyt...Figure 4.24 Structures of the three‐center halogen‐bonded (a) dimeric and (...Figure 4.25 Crystal structures of three‐center halogen‐bonded (a) dimeric c...Figure 4.26 Crystal structure of the three‐center halogen‐bonded helix. Cou...Figure 4.27 Crystal structures of the three‐center halogen‐bonded [R‐COOI...5 Chapter 5Figure 5.1 Decomposition of an experimental spectrum of a solution in liquid...Figure 5.2 Gogoi's 2‐chloropyridine–ICl complex.Figure 5.3 Halogen bond complex of molecular iodine and tetramethylthiourea....Figure 5.4 Hydrogen bonding of triethylamine with chloroform (a) versus halo...Figure 5.5 Huber's 2‐haloimidazolium salt and its interaction mode with a tr...Figure 5.6 Interactions of halogen bond donors with solvent molecules. Examp...Figure 5.7 Bowling's system for studying intramolecular halogen bonding.Figure 5.8 β‐Hairpin peptide displaying interstrand halogen bonding.Figure 5.9 Multidentate halogen bonding systems developed by Huber et al. Wh...Figure 5.10 Intramolecular hydrogen bonded–halogen bond in anion binding.Figure 5.11 An example of Diederich's supramolecular capsules held together ...Figure 5.12 Diederich's strong halogen bonding system, where 4‐(2‐iodoethyny...Figure 5.13 Representation of van't Hoff analysis of Diederich's halogen bon...Figure 5.14 Beer's halogen bond acyclic receptor (to the left) that complexe...Figure 5.15 Chemical double‐mutant cycle containing a potential halogen bond...Figure 5.16 Example of a Job plot showing 1 : 1 stoichiometry of binding, wi...Figure 5.17 Taylor's tridentate halogen bond donor, with three separate halo...Figure 5.18 Halogen bond complex of 4‐methylpyridine and Philp's iodotriazol...Figure 5.19 An example of Rissanen's N‐halosaccharin‐pyridine N‐oxide haloge...Figure 5.20 Monomers of Jiang's two halogen bonding systems. Top: two repres...Figure 5.21 Berryman's halogen bonding triple helicate from a side‐on perspe...Figure 5.22 Schubert's double bidentate system displaying an orthogonal arra...Figure 5.23 Main NOEs seen in a 1H,19F HOESY experiment by Ciancaleoni et al...Figure 5.24 Beer's macrocyclic haloimidazolium anion receptor in solution, r...Figure 5.25 Philp's iodotriazole dimer in solution.Figure 5.26 Erdelyi's symmetric [NXN]+ system, with 3‐center‐4‐electro...Figure 5.27 TEMPO radical resonance forms.Figure 5.28 Micallef's halogen bond complex of (TMIO)2‐DITFB.Figure 5.29 Lucarini's organic radical probe displaying halogen bonding to q...
6 Chapter 6Scheme 6.1 Examples of artificial and naturally occurring anion transporters...Scheme 6.2 Synthesis of calix[4]arene‐based transporters 10–13. (a) A...Figure 6.1 (a–f) DTF (PBE1PBE/6‐311G**) optimized TMACl complexes of calix[...Scheme 6.3 Synthesis of oxacalix[2]arene[2]triazine‐based transporters 18–2...Figure 6.2 Examples of the use of crystallography to help elucidate the rol...Figure 6.3 The HPTS assay. (a) Schematic representation of the HPTS assay in...Figure 6.4 Schematic representation of symport and antiport transport mechan...Scheme 6.4 Molecular structures of the small molecules tested as halogen bon...Figure 6.5 Conductance experiments in planar lipid bilayer membranes. (a) T...Figure 6.6 (a) Evolution of the effective molar concentration to achieve 50...Scheme 6.5 Synthesis of rigid‐rod p‐oligophenyl‐based transporters 47–54...Figure 6.7 (a,b) Evolution of the effective molar concentration to achieve ...Scheme 6.6 Synthesis of the library of pore‐forming peptides tested by Zeng ...Scheme 6.7 Molecular structures of the pore‐forming peptides used by Zeng an...Figure 6.8 (a) Computationally optimized H‐bonded octamer formed from pore‐...
7 Chapter 7Scheme 7.1 Selected examples for stoichiometric applications of iodine in or...Scheme 7.2 The first iodine‐catalyzed reaction. (Hibbert [10a] and Conant an...Scheme 7.3 Suggested activation mechanisms of molecular iodine with a typica...Figure 7.1 Crystal structures and selected bond lengths (in Å) featuring int...Scheme 7.4 Selected association constants and energies (in kJ/mol) for the i...Figure 7.2 Crystal structures and selected bond lengths (in Å) of interactio...Scheme 7.5 Equilibrium constants for the heterolytic cleavage of molecular i...Scheme 7.6 Iodine splitting in the presence of aza‐crown ethers. (Hasani and...Scheme 7.7 Potential decomposition reactions of molecular iodine in aqueous ...Scheme 7.8 Latimer diagrams with the standard potentials (in V) for iodine a...Scheme 7.9 Selected examples for iodine‐catalyzed Michael additions. (Banik ...Scheme 7.10 Iodine‐catalyzed Michael additions between indoles and α,β‐unsat...Scheme 7.11 Calculated effect of halogen bonding by molecular iodine on the ...Scheme 7.12 Examples for iodine‐catalyzed Knoevenagel condensations. (Ren an...Scheme 7.13 Example for an iodine‐catalyzed hetero‐Diels–Alder reaction. (Li...Figure 7.3 Iodine‐catalyzed carbonyl‐olefin metathesis. (Tran et al. [49c].)...Scheme 7.14 Iodine‐mediated cyclopropanation with the proposed mechanism. (L...Scheme 7.15 Iodine‐mediated synthesis of pyrroles. (Li et al. [50].)Scheme 7.16 Proposed reaction mechanism for the iodine‐catalyzed diaza‐Nazar...Figure 7.4 Iodine‐catalyzed Nazarov cyclizations. (Koenig et al. [53].)Scheme 7.17 Examples for iodine‐catalyzed esterifications and transesterific...Scheme 7.18 Examples for iodine‐catalyzed ester hydrolysis of biomolecules. ...Scheme 7.19 Iodine‐catalyzed acetalizations and deacetalizations. (Kumar et ...Scheme 7.20 Examples for iodine‐catalyzed synthesis of 1,1‐diacetates and di...Scheme 7.21 Iodine‐catalyzed etherifications [58,72,73].Scheme 7.22 Examples for iodine‐catalyzed Friedel–Crafts alkylations [75–77]...Scheme 7.23 Examples for iodine‐catalyzed Friedel–Crafts acylations [79–81]....Scheme 7.24 Iodine‐catalyzed isomerization of 1‐butene and cis‐2‐butene to t...Scheme 7.25 cis–trans Isomerization of fatty acid derivatives in the p...Scheme 7.26 Proposed reaction mechanism for the iodine‐catalyzed isomerizati...Scheme 7.27 Iodine‐catalyzed dimerization of 1,1‐diphenylethene. (Evans et a...Scheme 7.28 Iodine‐mediated cationic polymerization of furfuryl alcohol. (Go...Scheme 7.29 Proposed reaction mechanism for an iodine‐catalyzed Povarov reac...Scheme 7.30 Iodine‐catalyzed synthesis of dihydropyridines. (Ko et al. [99]....Scheme 7.31 Iodine‐catalyzed synthesis of trans‐fused pyrano[3,2‐c]benzopyra...Scheme 7.32 Iodine‐catalyzed cascade reaction for the synthesis of spirodihy...Scheme 7.33 Iodine‐mediated pyrrole activation ([102,103], MW: microwave irr...Scheme 7.34 Proposed mechanism for the iodine‐catalyzed quinoline synthesis....
8 Chapter 8Scheme 8.1 Outline of transient XB catalysis in halogenation/halocylizations...Scheme 8.2 XB‐promoted photochemical reactions.Figure 8.1 General outline of XB‐induced organocatalysis.Scheme 8.3 XB‐induced halide abstraction reactions. (a) Ritter‐type reaction...Figure 8.2 Cationic XB donors.Figure 8.3 Neutral multidentate XB donors.Scheme 8.4 Reactions involving XB‐catalyzed halide abstraction. (a) Halide a...Scheme 8.5 XB‐mediated polymerizations. (a) Neutral group activation.(b)...Scheme 8.6 Reduction of quinolones through XB interaction. (a) Neutral XB do...Scheme 8.7 XB‐catalyzed Diels–Alder reactions. (a) Diels–Alder reaction. (b)...Scheme 8.8 XB‐catalyzed Michael addition of indoles.Scheme 8.9 XB‐catalyzed conjugate addition of thiophenes.Scheme 8.10 XB‐promoted Nazarov cyclization..)Scheme 8.11 Friedel–Crafts alkylation of indoles with aldehydes and ketones....Scheme 8.12 Multistage strain‐release glycosylation through XB.Scheme 8.13 Bromocarbocyclization via halogen bonding.Scheme 8.14 Diaryliodonium‐salt‐catalyzed three‐component Mannich reac...Figure 8.4 Iodine (III) derivatives used as halogen bonding organocatalysts....Scheme 8.15 Umpolung CC bond formation involving an iodolium ylide‐halogen ...Scheme 8.16 Iodoalkyne‐induced activation of thioamides.Scheme 8.17 Organocatalysis by neutral C(sp3)–halogen‐based XB donors. (a) S...Scheme 8.18 XB‐catalyzed organocatalysis in water by an amino acid‐based XB ...Figure 8.5 Tetrapodal XB donor showing strong halide binding in water.Scheme 8.19 XB‐promoted selective oxidation of aryl(heteroaryl)methanes.Scheme 8.20 [4 + 2] Cycloaddition reactions via XB‐π activation.Figure 8.6 Triazolium‐based chiral XB donors.Scheme 8.21 Bis(imidazolium)‐based bidentate chiral XB donors in asymmetric ...Scheme 8.22 Chiral pentanidium
