From Monofunctional to Unconventional Bifunctional Organocatalytic systems

Résumé

The work compiled in this doctoral thesis is focused on Organocatalysis and contains four chapters. Along these chapters, different asymmetric and organocatalytic methodologies have been developed, in order to obtain organic compounds with valuable pharmaceutical and industrial properties. Each of the four chapters of this thesis presents independent enumeration. The new products obtained in this PhD. have been assigned with latins numbers, the compounds described in the literature with letters and the reaction intermediates with romans numbers. In the first chapter, we have developed a methodology for the synthesis of enantioenriched 2,3-diheteroarylalkanals employing aminocatalysis. The desired products have tremendous importance as natural products. We have also carried out the antiproliferative analysis of the new compounds. In chapter two, a review of the Vinylogous Mukaiyama is presented. It is shown all the different modes of activation of this reaction as well as all the advantages and drawbacks of every method described. In chapter three, we have shown that in the presence of a bifunctional catalysts it is possible to change the regioselectivity of the silyl-dienol ethers from 1,5 to the 1,3 functionalization.. This fact makes possible the access to a wide range of Rauhut-Currier type-products, with good yields and excellent enantioselectivities. In the last chapter, we have expanded the methodology described in the previous chapter, but in this case employing imines as the electrophile, obtaining a general method for the enantioselective synthesis of aza-Baylis-Hillman type-products, which most of them are difficult to achieve by other convenctional methods.