Browsing by Author "Oksanen, Valtteri"

Catechol is widely produced platform chemical, and many fine chemicals, including pharmaceuticals and pesticides, contain catechol moieties. Catechols are nucleophilic, but their polarity can be reversed by oxidizing them into electrophilic o-benzoquinones (OBQs). OBQs are highly reactive and react readily with nucleophiles but also with dienes, dienophiles and ylides. However, OBQs have many reactive sites, which often leads to lack of selectivity in reactions. In the literature review of this thesis, the methods to control selectivity in nucleophilic additions, cycloadditions and Wittig reactions of OBQs are reviewed. Selectivity is often increased by blocking undesired reactive sites by substituents. If substituents can’t be altered, it is possible to control selectivity by choice of catalysts and substrates as well as stoichiometric ratios of substrates. In addition, the literature review will also focus on how the use of o-benzoquinones have been utilized in organic synthesis. In the experimental part, nucleophilic additions of amino acids and silyl enol ethers to o-benzoquinones are studied in practice. Reactions of amino acids with OBQs resulted only in polymerization despite the efforts to control the selectivity. However, ZnCl2 catalysed addition of silyl enol ethers into OBQs yielded only 1,4-addition products. The method was then optimized with two model reactions after which 30 different 1,4-addition products were successfully synthesized. For most of these products this method is the only proven synthesis route.