Halogen Bonding in Solution

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 libraryof 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 CC bond formation involving an iodolium ylide‐halogen ...Scheme 8.16 Iodoalkyne‐induced activation of thioamides.Scheme 8.17 Organocatalysis by neutral C(sp 3)–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 salts as phase‐transfer catalysts.Scheme 8.23 XB‐catalyzed asymmetric Michael–Henry reaction in synthesis of t...Scheme 8.24 Enantioselective Mannich reactions with a quinidine‐based cataly...Scheme 8.25 S N2(X) reaction with subsequent chirality transfer via ion pairi...Scheme 8.26 XB‐induced preorganization of chiral catalysts.Scheme 8.27 XB‐assembled bidentate phosphine complexed Rh(I) catalysts.Figure 8.7 Stabilization of reaction precursors through XB.Scheme 8.28 XB template‐induced macrocyclization.Scheme 8.29 Thiourea/XB donor cocatalysis for direct N ‐glycofunctionalizatio...

9 Chapter 9Figure 9.1 (a) Cyclic voltammograms of TCQin the presence of increasing met...Figure 9.2 Chemical structures of IEDT and diodo(ethylenedithio)tetrathiaful...Figure 9.3 Concept of electrochemical XB activation.Figure 9.4 Cyclic voltammograms of TCQ(0.5 mM) on a glassy carbon electrode...Figure 9.5 (a) Variation of the potential shift (Δ E° ) corresponding to ...Figure 9.6 Ferrocene‐based XB donor receptors.Figure 9.7 SWV of 3‐XB‐Fc(a) and 3‐HB‐Fc(b) (0.25 ...Figure 9.8 Structure and design features of the target all‐XB redox‐active [...Figure 9.9 TTF derivatives.Figure 9.10 (a) Electrostatic surface potentials of 1‐TTF. (b) Stabili...Figure 9.11 (a) CV of 1‐TTF(left) and 2‐TTF(right) (0.25 mM) o...Figure 9.12 (a) Dependence of the first oxidation potential shift (Δ E ′) of 1...Figure 9.13 (a) Variation of the potential shift (Δ E 0′) of the first w...Figure 9.14 Bipyridinium derivatives. (Mullaney et al. [51]; Creste et al. [...Figure 9.15 (a) CVs of 2‐XB‐MV(0.25 mM) on a glassy carbon elec...Figure 9.16 CVs of SAMs of SAM‐4‐TTF(a) and SAM‐5‐TTF...Figure 9.17 Principle of electrochemically driven XB formation in the presen...Figure 9.18 (a) Schematic representation of the foldamer SAM on a gold elect...Figure 9.19 (a) Molecular structure of the titanium dioxide grafted dye (X =...Figure 9.20 (a) Proposed mechanism for XB‐assisted ET between NO 2‐CBr 3(R–Br...