Automated glycan assembly (AGA) is contingent on the development of simple, efficient cleavage strategies to liberate complex, high value products from a solid support resin. Given the rapid advances in the structural complexity of carbohydrates that can be constructed via this enabling technology, effective cleavage is a persistent challenge. Photolabile linkers have a venerable history in AGA and mitigate potential complications arising from chemically induced release protocols. However, photochemical cleavage strategies have traditionally relied upon mercury vapor lamps, which present challenges in establishing welldefined, reproducible, and nonhazardous conditions for this ultimate step of the AGA sequence. To complement the existing batch strategies, a safe and sustainable approach for the continuous flow photocleavage from solid support using LEDs has been developed. By employing a custom-built LED flow reactor, photocleavage yields of up to 80% were achieved in less than 1 h. Efficiency could be further improved by merging flow photochemistry with pregrinding. Validation of this strategy is showcased in a proof of concept AGA synthesis of a model dimannoside.

A series of five 12-dodecanolides have been synthesised containing CF 2 groups at C5, C6, C7, C8 and in one case a double substitution at C5 & C8, as a strategy to bias the conformational space accessed by these macrocycles, and to assess if the analogues may act as mimetics for 12-decenolide pheromones associated with the Emerald Ash Borer.

This short review surveys aspects of glycolipid-based natural products and their biological relevance in multiple sclerosis (MS).

Automated glycan assembly (AGA) on solid support has become invaluable in reconciling the biological importance of complex carbohydrates with the persistent challenges associated with reproducible synthesis. Whilst AGA platforms have transformed the construction of many natural sugars, validation in the construction of well-defined (site-selectively modified) glycomimetics is in its infancy. Motivated by the importance of fluorination in drug discovery, the biomedical prominence of 2-fluoro sugars and the remarkable selectivities observed in fluorine-directed glycosylation, fluorine-directed automated glycan assembly (FDAGA) is disclosed. This strategy leverages the fluorine atom for stereocontrolled glycosylation on solid support, thereby eliminating the reliance on O-based directing groups. The logical design of C2-fluorinated mannose building blocks, and their application in the fully (α-)stereocontrolled automated assembly of linear and branched fluorinated oligomannosides, is disclosed. This operationally simple strategy can be integrated into existing AGA and post-AGA protocols to augment the scope of programmed carbohydrate synthesis.