Regioselective oxidation of unprotected 1,4 linked glucans

Palladium-catalyzed alcohol oxidation allows the chemo- and regioselective modification of unprotected 1,4 linked glucans. This is demonstrated in the two-step bisfunctionalization of 1,4 linked glucans up to the 7-mer. Introduction of an anomeric azide is followed by a highly regioselective mono-oxidation of the terminal C3-OH functionality. The resulting orthogonal bis-functionalized oligosaccharides are a viable alternative to PEG-spacers as demonstrated in the conjugation of a cysteine mutant of 4-oxalocrotonate tautomerase with biotin

On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides

The palladium-catalyzed oxidation of glucopyranosides has been investigated using relativistic density functional theory (DFT) at ZORA-BLYP−D3(BJ)/TZ2P. The complete Gibbs free energy profiles for the oxidation of secondary hydroxy groups at C2, C3, and C4 were computed for methyl β-glucoside and methyl carba-β-glucoside. Both computations and oxidation experiments on carba-glucosides demonstrate the crucial role of the ring oxygen in the C3 regioselectivity observed during the oxidation of glucosides. Analysis of the model systems for oxidized methyl β-glucoside shows that the C3 oxidation product is intrinsically favored in the presence of the ring oxygen. Subsequent energy decomposition analysis (EDA) and Hirschfeld charge analysis reveal the role of the ring oxygen: it positively polarizes C1/C5 by inductive effects and disfavors any subsequent buildup of positive charge at neighboring carbon atoms, rendering C3 the most favored site for the β-hydride elimination

Manganese-Catalyzed Dihydroxylation and Epoxidation of Olefins

The oxidation of alkenes to epoxides and diols is a key functional group transformation in organic chemistry opening the way to a wide range of further derivatizations. Achieving these transformations with atom efficiency necessitates the use of catalysts, and in this aspect manganese complexes have stood out over the last decades for the enantioselectivities that can be achieved and the often high turnover numbers and frequencies possible. In this chapter, the scope of manganese-catalyzed oxidation of alkenes is discussed from the perspective of mechanism with the goal of showing the diversity in reactivity that is already apparent.</p

Manganese-Catalyzed Dihydroxylation and Epoxidation of Olefins

The oxidation of alkenes to epoxides and diols is a key functional group transformation in organic chemistry opening the way to a wide range of further derivatizations. Achieving these transformations with atom efficiency necessitates the use of catalysts, and in this aspect manganese complexes have stood out over the last decades for the enantioselectivities that can be achieved and the often high turnover numbers and frequencies possible. In this chapter, the scope of manganese-catalyzed oxidation of alkenes is discussed from the perspective of mechanism with the goal of showing the diversity in reactivity that is already apparent

Formation of substituted dioxanes in the oxidation of gum arabic with periodate

Renewable polysaccharide feedstocks are of interest in bio-based food packaging, coatings and hydrogels. Their physical properties often need to be tuned by chemical modification, e.g. by oxidation using periodate, to introduce carboxylic acid, ketone or aldehyde functional groups. The reproducibility required for application on an industrial scale, however, is challenged by uncertainty about the composition of product mixtures obtained and of the precise structural changes that the reaction with periodate induces. Here, we show that despite the structural diversity of gum arabic, primarily rhamnose and arabinose subunits undergo oxidation, whereas (in-chain) galacturonic acids are unreactive towards periodate. Using model sugars, we show that periodate preferentially oxidises the anti 1,2-diols in the rhamnopyranoside monosaccharides present as terminal groups in the biopolymer. While formally oxidation of vicinal diols results in the formation of two aldehyde groups, only traces of aldehydes are observed in solution, with the main final products obtained being substituted dioxanes, both in solution and in the solid state. The substituted dioxanes form most likely by the intramolecular reaction of one aldehyde with a nearby hydroxyl group, followed by hydration of the remaining aldehyde to form a geminal diol. The absence of significant amounts of aldehyde functional groups in the modified polymer impacts crosslinking strategies currently attempted in the preparation of renewable polysaccharide-based materials