Computacional studies on the mechanism of the pauson-khand reaction

Identificador:  TDX:890

Handle: https://hdl.handle.net/20.500.11797/TDX890

Autors:  Fjermestad, Torstein

Resum:
The application of computational methods has lead to a better understanding of the mechanism of the Pauson-Khand reaction (PKR) for the synthesis of cyclopentenone compounds. In particular the enantioselective PKR has been considered. <br/><br/>Different methods for inducing enantioselectivity in this originally unselective reaction have been analyzed. Three cases have been considered: a) Activation of the conventional dicobalt octacarbonyl catalyst by a chiral N-oxide, b) A modification of the dicobalt catalyst by means of a substitution of two carbonyl ligands by a chiral diphosphine ligand. and c) the substitution of the dinuclear cobalt catalyst by a mononuclear rhodium catalyst with chiral ligands. <br/><br/>The theoretical study has lead to the characterization of mechanistic aspects that would be inaccessible from a purely experimental study. The study therefore contributes to the development of more efficient catalytic methods for this important reaction.