Click chemistry is used to functionalize simple lipophilic and water-soluble molecules, a complex PEGylated phospholipid (DSPE-PEG2000), and two benzylic substrates with the 2-(hydroxyimino)aldehyde (HIA) group. To this end, two terminal alkynes bearing the HIA moiety were synthesized and coupled to different azides through copper(I)-catalyzed azide alkyne cycloaddition (CuAAC). Norrish-Yang photoisomerization (?= 365 nm, LED source) is successfully obtained, with no interference by the triazole linker, except when the forbidden n-?* carbonyl transition is screened by a remote substituent such as salicylaldehyde. UV-Vis spectrometry suggests a specific interaction of HIAs with Cu(II), whereas no such evidence is found with Cu(I). We thereby show that the CuAAC methodology can be used successfully to obtain HIA-based UV-responsive hydrophilic or lipophilic ligands, phospholipidic components for the construction of liposomes, and macrocycle precursors.
Click-Connected 2-(Hydroxyimino)aldehydes for the Design of UV-Responsive Functional Molecules
D'Acunzo F;
2021
Abstract
Click chemistry is used to functionalize simple lipophilic and water-soluble molecules, a complex PEGylated phospholipid (DSPE-PEG2000), and two benzylic substrates with the 2-(hydroxyimino)aldehyde (HIA) group. To this end, two terminal alkynes bearing the HIA moiety were synthesized and coupled to different azides through copper(I)-catalyzed azide alkyne cycloaddition (CuAAC). Norrish-Yang photoisomerization (?= 365 nm, LED source) is successfully obtained, with no interference by the triazole linker, except when the forbidden n-?* carbonyl transition is screened by a remote substituent such as salicylaldehyde. UV-Vis spectrometry suggests a specific interaction of HIAs with Cu(II), whereas no such evidence is found with Cu(I). We thereby show that the CuAAC methodology can be used successfully to obtain HIA-based UV-responsive hydrophilic or lipophilic ligands, phospholipidic components for the construction of liposomes, and macrocycle precursors.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
