Synthesis and Azobenzene Isomerization Investigation of Photoswitchable Glycomacrocycles.

Macrocyclic glycoazobenzenes, as an emerging class of photoswitchable chiral macrocyclic compounds, have shown interesting properties since their discovery in 2017. We have recently employed the azobenzene-ester-linked glycosyl donor-acceptor pairs to study the influence of photoisomerization on intramolecular glycosylation. To continue the investigation on the stereoselectivity aspect of glycosylation and also to enlarge the diversity of photoswitchable glycomacrocycles, we have chosen azobenzene-triazole linkers in the present study and shown that the stereoselectivity of the glycosylation is dependent on the linker length, the configuration of the azobenzene template, as well as the reaction concentration. We have optimized the reaction conditions to prepare in good yields new glycomacrocycles, which displayed excellent photochromic properties. The influence of glycosylation reagents and acidity on the stability of the Z -azobenzene substrates and cyclic glycoazobenzenes has also been investigated, demonstrating that isomerization of macrocyclic azobenzene can be tuned by photo-, thermo-, and acid stimulus.