[3+2] Cycloadditions, Mannich and Morita-Baylis-Hillman reactions involving N-tert-butanesulfinyl imines

Different methodologies using chiral N-tert-butanesulfinyl imines as valuable starting materials to obtain new families of valuable structures will be presented in this dissertation. This work has been divided into four main chapters and a general introduction: - In the general introduction different concepts like asymmetric synthesis, the use of chiral auxiliaries, the applications of N-tert-butanesulfinyl imines and the literature precedents of the main reactions studied will be introduced. - In the first chapter, the stereoselective synthesis of densely substituted pyrrolidines via a [3+2] cycloaddition reaction between chiral N-tert- Butanesulfinylazadienes and azomethine ylides by using silver carbonate as catalyst, the synthesis of a wide variety of proline derivatives with high regio- and diastereoselectivities has taken place. Subsequent transformations such as intramolecular cyclizations have provided a new family of molecules with potential applications in the pharmaceutical industry. - Encouraged to avoid the use of metals and have faster reaction conditions, in Chapter II the use of isatins and L-proline to generate the 1,3-dipole will be studied by using again the N-tert-Butanesulfinylazadienes as dipolarophiles. This project avoids the use of metals and adds the use of a greener solvent compared to the previous chapter in low quantities. The products will be obtained in high yields and diastereoselectivities and due to their structure, they will be presented as potential drugs candidates. - The deacetylative protocol to obtain α-fluoro-β-amino-indolin-2-ones via Mannich reaction in a diastereoselective way by using aliphatic N-tert-butanesulfinyl imines will be discussed on Chapter III. For that, the need of a base is required to form the deacetylated product that will react in high diastereoselectivities. The differences between previous described protocols will be compared. - In the last chapter a new approach in the Morita-Baylis-Hillman reaction will be explained by using activated terminal alkenes with N-tert-butanesulfinyl imines as electron-withdrawing group and a novel rearrangement will be described.

Author

• Blanco-López, Ester

• [3+2] Cycloaddition
• Azometine ylide
• Dipolarophile
• 1
• 3-dipolar
• Mannich reaction
• Diastereoselective
• Asymmetric synthesis
• Morita-Baylis-Hillman reaction
• N-tert-butanesulfinyl imine

Identifier

hdl:10045/162768

OAI identifier oai:identifier

oai:rua.ua.es:10045/162768