In this Project, we will carry out a mechanistic study of cyclopropanation reactions, including catalytic processes and rections of \alpha-phosphamino diazoalkanes and carbenes. Several photochemical processes will also be investigated involving pyrazoline stereospecific photolysis, chiral olefin photoisomerization, and [2+2] cycloadditions to cyclic or acyclic substrates. In addition on the corresponding experiments, DFT and CASSCF theoretical calculations will be done. Besides these studies, the asymmetric synthesis of cyclopropane or cyclobutane derivates will be archieved. Among these compounds, amino acids peptides, pseudopeptide nucleic acid monomers, and fullerene derivates are prominent. As the most relevant protocols, the hydrogenation of chiral substrates employing chiral catalysts and the stereospecific addition of N-alkyhydroxylamines to chiral olefines are remarkable. Furthermore, the structural study of \beta and \gamma-peptides will be realized by using chiroptical and spectroscopic techniques, as well as theorical calculations (DFT, molecular dynamics). Finally, the biological activity of several selected products will be tested.
|Effective start/end date||28/12/01 → 27/12/04|