March 2022

We recently discovered a functional group tolerant and transition-metal-free conjunctive olefination reaction with applications in late-stage functionalization chemistry. In this Synpacts contribution, we analyze the conceptual background that has stimulated the discovery of this reactivity and reflect on the key aspects of its development.1 Introduction2 Conceptual Background2.1 Photoredox-Mediated Giese Reaction2.2 Photoredox Radical-Polar Reactivity3 The Development of the Process4 Conclusion

Modifications of glycosidic linkers are valuable in medicinal chemistry and natural-product synthesis. Whereas considerable attention has been paid to the development of methods for monoglycosylation, the corresponding geminal diglycosylation has almost been ignored. Little work has focused on exploring new routes for stereoselective gem-diglycosylation, presumably due to challenges in controlling selectivity and activity on a confined quaternary carbon center. Highlighted herein is a recent advance in stereoselective C,B-glycosylation through an unprecedented PPh3-promoted 1,2-boronate-migration process.

Synlett 2022; 33: V-DOI: 10.1055/s-0041-1737399Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, GermanyArticle in Thieme eJournals:Table of contents