This Doctoral Thesis is aimed to discuss the latest developments in the field of oxidative carbon-nitrogen bond construction. Alternatives to established synthetic methodologies have been disclosed with the use of hypervalent iodine reagents and molecular iodine as main promoters.
Initially, the use of defined hypervalent iodine reagents that promote the selective direct C-H-amination at the indole core of various tryptamines is presented. Starting from the general amination, subsequent transformations, such as iodination, fluorination etc. afford higher-functionalized products with a noteworthy chemoselectivity. Consequently, a higher degree of structural diversification has become available for tryptamine derivatives. Subsequently, a photochemical catalytic amination of arenes is discussed. The reaction proceeds under benign iodine catalysis in the presence of visible light as the initiator and provides access to a range of differently substituted arylamines. A different approach for the synthesis of 3-substitued anilines is presented as well.
The direct amination of aliphatic C-H bonds has remained one of the most challenging transformations in organic chemistry. In the last part, the elusive intermolecular C(sp3)-H amination based on a unique homogeneous iodine catalyst system is reported. This practical synthetic strategy allows the access to aminated building blocks. An extension that fosters innovative multiple C-H amination toward N-heterocycles is also presented. The synthetic utility of the methodology is demonstrated by the synthesis of relevant pharmaceuticals.