Rh-catalyzed carbonylation of disubstituted olefins: asymmetric catalysis, continuous flow and tandem hydroaminomethylation reaction

Identifier:  TDX:2927

Handle: https://hdl.handle.net/20.500.11797/TDX2927

Authors:  Cunillera Martin, Anton

Abstract:
The current Ph. D. Thesis deals with the carbonylation of disubstituted olefins. The impact of the alkene carbonylation reactions is stressed; especially the most important results in asymmetric hydroformylation and hydroaminomethylation reported in the literature are described. Furthermore, a description of flow systems and the benefits of its implementation to catalytic processes are detailed. In Chapter 3 the rhodium catalyzed asymmetric hydroformylation of norbornene in batch and under flow conditions using heterogenized catalysts is described. In Chapter 4 it is detailed the rhodium catalyzed asymmetric hydroaminomethylation of acrylates for the efficient synthesis of chiral gamma-aminobutyric esters. This system constitutes the first example of asymmetric hydroaminomethylation of olefins catalyzed by one single rhodium precursor. Furthermore, the results obtained via high pressure NMR in the study of the reactivity of the catalytic systems are described. Finally, the Chapter 5 presents the results obtained in the rhodium catalyzed regioselective hydroaminomethylation of acrylates for the synthesis of beta-amino esters, as well as the different effects observed when primary and secondary amines area applied.