One-Pot Synthesis of Water-Soluble Glycosyl Azobenzenes and Their Photoswitching Properties in Water.

Abstract

Molecular photoswitches capable of reversible photoswitching in aqueous media are highly demanded for various biological applications and photopharmacology. Carbohydrates, as natural and abundant raw materials, provide opportunity to make photoswitches water-soluble through linking sugar to the photoswitching molecules. We have developed a one-pot synthesis method to prepare water-soluble glycosyl azobenzenes through DMC (2-chloro-1,3-dimethylimidazolinium chloride)-mediated glycosylation between sugar and dihydroxyazobenzenes (DHABs) in aqueous media. The scope of the method has been investigated with different mono- and disaccharides, as well as with p,p'- and o,o'-DHAB, with excellent 1,2-trans stereoselectivity. Diglycosylation products can also be obtained with an excess amount of monosaccharides in one step. We have also demonstrated the possibility of further functionalization on the azobenzene moiety of glycosyl azobenzene. Both mono- and diglycosyl azobenzenes showed excellent photoswitching properties in water with high fatigue resistance and good thermostability for the Z-isomers. Excellent E → Z photoisomerization of both mono- and diglycosylated azobenzenes (Z/E = 99/1) is observed under illumination at 365 nm, while back Z → E photoisomerization can be achieved with blue light (with E/Z = 80/20 at PSS485 for the diglycosyl derivative).