The glycosylation of O-glycosyl trichloroacetimidate donors using a synergistic catalytic system of electron-deficient pyridinium salts/aryl thiourea derivatives at room temperature is demonstrated. The acidity of the adduct formed by the 1,2-addition of alcohol to the electron-deficient pyridinium salt is increased in the presence of an aryl thiourea derivative as an hydrogen-bonding cocatalyst. This transformation occurs under mild reaction conditions with a wide range of O-glycosyl trichloroacetimidate donors and glycosyl acceptors to afford the corresponding O-glycosides in moderate to good yields with predictable selectivity. In addition, the optimized method is also utilized for the regioselective O-glycosylation by using a partially protected acceptor.
An
efficient and operationally simple gold(III)-catalyzed glycosylation
protocol was developed using newly synthesized benchtop stable phenylpropiolate
glycosyl (PPG) donors. Gold(III)-catalyzed activation of PPGs proceeds
well with various carbohydrate and noncarbohydrate-based glycosyl
acceptors and leads to their corresponding O/N-glycosides in good to excellent yields with regeneration
of reusable and easily separable phenylpropiolic acid. Differentially
protected PPGs reacted well under the optimized reaction conditions.
In particular, good anomeric selectivity was observed with mannosyl
and rhamnosyl PPG donors. A preliminary mechanistic study reveals
that the presence of a triple bond adjacent to the ester group is
essential for activation, and PPG-based donor shows higher reactivity
than analogous acetate and benzoate donors.
A straightforward
route has been developed for the diastereoselective
synthesis of nonclassical conformationally constrained oxazoline-fused
and spiro bicyclic sugars bearing a quaternary center via selective
β-C–H amination of appropriately positioned glycosylimidates.
The desired transformation proceeds via the generation of imidate
N-radicals under visible-light conditions followed regioselective
intramolecular N–C bond formation. The reactions tolerate broad
functional groups under the optimized conditions. Furthermore, the
synthetic utility of oxazoline-fused bicyclic sugar moiety is demonstrated
through the glycosylation reactions.
A simple and straightforward method for the synthesis of primary α-ketoamides has been discovered. The reaction represents the first example of benzylimidates directly converting to primary α-ketoamides by using sustainable molecular oxygen as an oxidant. This reaction proceeds in the presence of copper(II) salt via cleavage of benzylic C-H and C-O bonds of the benzylimidates with liberation of alcohols as the only byproduct. A wide substrate scope, operationally mild conditions, the use of single substrates, and a reaction scaled up to grams make this strategy very attractive and practical. Furthermore, mechanistic studies illustrate that the imidate group adjacent to the benzylic position plays crucial role in facilitating this chemical process.
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