Self‐promoted glycosylation using trichloroacetimidates and sulfonamides have recently been developed. In this communication, we study the parameters controlling the chemoselectivity between a nucleophilic sulfonamide nitrogen and an alcohol, both contained in the same molecule. The influence of solvent polarity and concentrations have been studied, and it has been revealed how the chemoselectivity, and to some extend the stereoselectivity, can be controlled. The experimental results furthermore provide insight into the reaction mechanism of this self‐promoted glycosylation and the mechanism of glycosylation reactions in general.

Levulinic acid, which is one of the most important renewable building blocks derived from lignocellulosic biomass, has been converted in a diversity‐oriented manner into two families of drug‐like bicyclic nitrogen heterocycles. The methodology, endowed with high step economy and operational simplicity, is based on an Ugi multicomponent reaction, which employs amino alcohols as components, followed by a SN2 cyclization. Noteworthy is the successful synthesis of hexahydro pyrrolodiazepinediones, since the cyclization of the isocyanide‐derived secondary amide onto an alcohol to give a seven‐membered ring was unprecedented. Also enantiopure products have been prepared by using chiral amino alcohols.

Starting from easily accessible enantiopure 1,2-aminoalcohols and salicylaldehydes, a concise and diastereodivergent route to tetrahydrobenzo[f][1,4]oxazepines has been developed.

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