A Unified Strategy to Access 2- and 4-Deoxygenated Sugars Enabled by Manganese-Promoted 1,2-Radical Migration.

The selective manipulation of carbohydrate scaffolds is challenging due to the presence of multiple, nearly chemically indistinguishable O-H and C-H bonds. As a result, protecting-group-based synthetic strategies are typically necessary for carbohydrate modification. Here we report a concise semisynthetic strategy to access diverse 2- and 4-deoxygenated carbohydrates without relying on the exhaustive use of protecting groups to achieve site-selective reaction outcomes.

Selective Transformations of Carbohydrates Inspired by Radical-Based Enzymatic Mechanisms.

Enzymes are a longstanding source of inspiration for synthetic reaction development. However, enzymatic reactivity and selectivity are frequently untenable in a synthetic context, as the principles that govern control in an enzymatic setting often do not translate to small molecule catalysis. Recent synthetic methods have revealed the viability of using small molecule catalysts to promote highly selective radical-mediated transformations of minimally protected sugar substrates.

Positioning-Group-Enabled Biocatalytic Oxidative Dearomatization.

Biocatalysts have the potential to perform reactions with exceptional selectivity and high catalytic efficiency while utilizing safe and sustainable reagents. Despite these positive attributes, the utility of a biocatalyst can be limited by the breadth of substrates that can be accommodated in the active site in a reactive pose. Proven strategies exist for optimizing the performance of a biocatalyst toward unnatural substrates, including protein engineering; however, these methods can be time intensive and require specialized equipment that renders these approaches inaccessible to synthetic chemists.

Novel carbohydrate binding modules in the surface anchored α-amylase of Eubacterium rectale provide a molecular rationale for the range of starches used by this organism in the human gut.

Gut bacteria recognize accessible glycan substrates within a complex environment. Carbohydrate binding modules (CBMs) of cell surface glycoside hydrolases often drive binding to the target substrate. Eubacterium rectale, an important butyrate-producing organism in the gut, consumes a limited range of substrates, including starch.