Organophotoredox-Catalyzed Formation of Alkyl–Aryl and −Alkyl C–S/Se Bonds from Coupling of Redox-Active Esters with Thio/Selenosulfonates

Dong, Yue; Ji, Peng; Zhang, Yueteng; Wang, Changqing; Meng, Xiang; Wang, Wei

doi:10.1021/acs.orglett.0c03624

Abstract The lyotropic properties of alkyl thioglycosides with varying sugar headgroup (lactose, cellobiose, maltose, galactose, or glucose) and alkyl chain length (octyl, decyl, or dodecyl chains) are investigated by surface tensiometry, visual observation, and fluorescence spectroscopy. The results substantiate that the glycosidic S‐linkage confers considerably different solution aggregation behavior on these surfactants relative to their O‐linked counterparts, where the properties of the latter are known. The materials properties of the aggregated structures from the alkyl thioglycosides vary considerably. Micelles are formed by octyl thiocellobioside and all alkyl thiomaltosides. Turbid aggregate solutions are formed by the alkyl thioglucosides and octyl thiogalactoside, whereas the longer chain alkyl thiogalactosides are minimally soluble. Fluorescence spectroscopy of these systems confirms their aggregation in lamellar‐like structures. The alkyl thiocellobiosides and alkyl thiolactosides form hydrogels from these low‐molecular weight materials at concentrations almost an order of magnitude lower than gels using other low‐molecular weight materials. Here, hydrogels form at concentrations <0.3 wt% with some forming hydrogels at concentrations as low as 0.03 wt% from alkyl thiocellobiosides and thiolactosides, with hydrogel properties differing significantly with this slight change in the sugar headgroup. Alkyl thiocellobiosides form a nanofiber network and alkyl thiolactosides form globular hydrogels. Overall, these results clearly document materials properties that can readily be controlled and designed depending on molecular structure.

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