Click chemistry macrocycle

Applications of click chemistry are already far too numerous to acknowledge by even offering an example fi om each area herein. Some of these areas include dendrimers, polypeptides, polymeric materials, conformationally restricted macrocycles, new ligand designs, and carbohydrates. One representative procedure is provided below. A related study describes sugar-based silica gels for use as hydrophilic interaction chromatography (HILIC) for separation of monosaccharides. ... 

The [14]thiatriphyrin(2.1.1) (47) possessing a 14 t-electron pathway within the macrocycle without an inner NH group has been synthesized but it is highly reactive to nucleophilic addition at the meso-position (12ACIE3360). Porphyrin-tetrathiarubyrin dyads, as energy acceptors, have been constructed via Click chemistry (13T7943). 

We have also elaborated another route to macrocyclic sucrose dimers. Monosilylated hexa-O-benzylsucrose, with free hydrojgrl group at the glucose end (24b), was converted into azidoacetylene 79 in a number of standard steps. Cyclization of 79 was achieved via a click chemistry route and provided dimer 80 or monomers 81a and 81b. Formation of the 1,5-triazole 81b was quite unexpected, since according to a well accepted mechanism only the 1,4 adduct should be formed. This might... 

Scheme 17 Synthesis of sucrose macrocycles by click chemistry. ...

Figure 10.11 Macrocyclization of peptides by click chemistry between propargylic acid residues and an azide- functionalized amino acid...

The covalent attachment of MN4-MC on the surface of CNTs has been another way of combining macrocyclic complexes and carbon supports to fabricate functional hybrid materials. Coates et al. [56] described the chemical modification of SWCNTs after their adsorption on GC electrode. The procedure consisted first in the electrochemical grafting of 4-azido benzenediazoium salt on the surface of CNTs, followed by a reaction with ethylpyridine through click chemistry. Finally, the attachment of a FePc was carried out by axial bonding to the pyridine group. An illustration of these steps can be seen in Fig. 9. The sensor was applied in the electrocatalytic detection of hydrazine, with a ten times improvement of the limit of detection over the surface without the CNTs. 

In this chapter, we highlight recent examples of the use of the mentioned click reactions as the macrocyclization reaction in several contexts. We exclude the following from the current review (i) cyclic structures in which part of the cyclic connection is formed by noncovalent bonds [26] (ii) the postmodification with CuAAC click chemistry of preformed macrocycles in order to introduce triazoles for functional applications [27, 28] and (iii) coordination polymers, or metal-organic frameworks, formed by clicked struts or ligands [29]. This chapter is structured in several subchapters according to the different classes of macrocycles obtained. 

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