The first 2^IB,3^IA-heterodifunctionalized β-cyclodextrin derivatives as artificial enzymes

Abstract

Novel 2,3-heterodisubstituted β-cyclodextrin derivatives were designed as artificial enzymes to degrade chemical warfare agents. One of them reduced the acetylcholinesterase inhibitory potential by soman faster than its monosubstituted analog.

Enzyme Mimics: Advances and Applications

“…More importantly, functionalisation of CDs enable desired chemical transformations to occur. By changing either the primary or secondary hydroxy groups on the exterior into other functional groups, effective synzymes can be created (Figure ) …”

“…[34] The hydroxy groups give them their hydrophilic character,m aking them soluble in water.M ore importantly,f unctionalisation of CDs enable desired chemical transformations to occur.B yc hanging either the primary or secondary hydroxy groups on thee xterior into other functional groups,effective synzymes can be created( Figure 1). [20,35] Calixarenes are another type of supramolecule with hydrophobic cavities. The cavities allow them to bind small molecules or ions, enabling them to be used as ligandst of orm aw ider ange of complexes.…”

Interactions of cyclodextrins and their derivatives with toxic organophosphorus compounds

“…Methyl iodobenzoates were introduced following this approach ( Scheme 7 , 33a , b ), unfortunately, degradation occurred during the final oxidation step to obtain the α-nucleophile group [ 87 ]. The 3-monosubstituted derivative 41 was successfully obtained starting from the partially-protected 2,6-dimethyl-β-CD ( Scheme 7 ) [ 88 ]. Finally, CDs bearing an oxime ( 36 and 39a ) or a hydroxamic acid ( 39b ) group in position 3 were prepared as previously described via an azide–alkyne cycloaddition ( Scheme 7 ) [ 76 , 80 ].…”

“…Another particularly convenient strategy to introduce two different groups on adjacent units of methylated β-CD relies on the use of DIBAL-H to produce 2 A ,3 B -diol 46 from TRIMEB ( Scheme 9 ) [ 90 ]. The two remaining free alcohols were then functionalized with the α-nucleophile and an imidazole group [ 88 ]. The acid–base dyad thus obtained is likely to improve the hydrolysis of nerve agents.…”

Structure–efficiency relationships of cyclodextrin scavengers in the hydrolytic degradation of organophosphorus compounds

“…Also the 1 H and 13 C NMR spectra showed chemical shifts attributable to the CH 2 groups linked to the imidazole and iodobenzoate moieties, similar to those observed for the precursor of 1 [33]. The subsequent deprotection and oxidation–hydrolysis reactions of derivatives 13 and 14 afforded scavengers 2 and 3 , respectively and were performed in one step using sodium periodate in acidic medium.…”