Design, synthesis and applications of novel hypervalent iodine reagents

Hypervalent iodine reagents are environmentally benign alternatives to heavy metal oxidants. They are widely used in organic synthesis not only because of the environmentally friendly nature but also due to their readily availability, selectivity and mild reaction conditions. Hypervalent iodine compounds are efficient reagents for a wide range of oxidative transformations such as oxidation of alcohols, phenol dearomatisation, functionalisation of carbonyl compound and alkenes, halogenation, oxidative heterocyclisation, and oxidative rearrangement reactions. In this thesis, novel electron-deficient chiral hypervalent iodine reagents have been designed and synthesised (Scheme i). The reactivity and selectivity of the newly synthesised reagents have been studied in several stereoselective oxidative transformations. Stereoselective oxidative rearrangement of alkenes into the corresponding α-aryl ketone (Scheme ii) was studied using chiral iodoarenes as organocatalysts. In addition, the same transformation was studied using electrochemically generated hypervalent iodine reagent. Finally, the design, synthesis, and characterisation of novel pseudocyclic hypervalent iodine reagents bearing heteroaryl carbonyl moieties is described (Scheme iii). The newly synthesised reagents showed similar and sometimes better reactivity than Koser’s reagent