Acyl-transfer reactions are of the most common transformations in organic synthesis, as well as in Nature. Due to their importance in biochemical and synthetic processes, these reactions have been widely studied. The acylation of alcohols is a common transformation that can be promoted by a variety of catalysts. Among them, donor-substituted pyridine derivatives, such as DMAP, play an important role as nucleophilic catalysts. In spite of the widespread use of the acylation reaction, conducting it in a substrate- or site-selective manner still represents a major challenge.<br/>During the development of catalysts for a site-selective acylation reaction (Scheme 1a), we found that there is a strong influence of various additives, such as catalysts and bases, which are usually added to the catalytic system, on the substrate- and site-selectivity. Accordingly, we examined the influence of different quantities of bases, different kinds of bases and different types of catalysts (derivatives of nucleophilic molecules, such as n-Benzylimidazole and pyridine), on the substrate-selectivity of mono-site substrate probes (Scheme 1b). Various consequences of these findings will be presented.

Influence of bases and catalysts on substrate-selectivity in a model acylation reaction

2019 Fall National Meeting

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.