Within this thesis, the synthesis of highly functionalized enantioenriched macrocycles was attempted and applications in catalysis were undertaken. For this purpose, a three-step synthetic procedure was developed focusing on the deconjugative isomerization of endocyclic unsaturated amides. Also, care was taken to introduce strong hydrogen-bond donor groups such as squaramide moieties on the chiral platforms and study their activity in organocatalysis.

In other independent studies, the decomposition of diazo reagents and the subsequent reactivity of the derived metal carbenes were investigated using as substrates alkene-containing strained oxacycles to explore ring expansion or cascade transformations. First, the combination of 3-gem-dialkyl 2-vinyl-oxetanes and acceptor(-acceptor) diazo reagents under copper catalysis led to the formation of functionalized tetrahydro oxepines via [2,3]-Stevens rearrangement. Also, the dual reactivity of diazo malonate was studied, used both as 1,3-dipoles and carbene precursors, in presence of hetero benzonorbornadienes and under ruthenium catalysis, to prepare polycyclic pyrazolidines in a three-step synthetic sequence.