Repositori URV

Identifier: TDX:775

Handle: https://hdl.handle.net/20.500.11797/TDX775

Authors:
Yañez Rueda, Xiomara

Abstract:
The Hydroacylation reaction is a rhodium-catalyzed reaction that allows to obtain ketones from the reaction of aldehydes and alkenes. The intramolecular version in order to obtain cyclopentanones has been widely studied in order to determine the mechanism and also with synthetic purposes. Cycles of 5, 6, 7 and 8 rings have been prepared using this reaction. This reaction has been made enantioselective by using chiral diphosphine ligands such as BINAP or duphos. The intermolecular hydroacylation reaction has been less studied because the importance of the competitive decarbonylation of the aldehyde, that avoids the hydroacylation reaction to proceed. Most studies have been oriented to avoid this competitive reaction, and the most successful methodology involves the formation of a quelating aldimine by reaction of the aldehyde with 3-metil-2-picoline.In this PhD work in 8 different chapters. The first one contains a review of the more relevant work in hydroacylation intra- and intermolecular. The second one describes the main objectives of the work in the context of recent bibliography. Chapters 3 and 4 study the use of Montmorillonite MK-10 in the hydroacylation intermolecular with two different purposes, to be the acid catalysts for the imine formation and ketimine hydrolysis and to the support in order to recover the catalysts. The behaviour as acid catalyst is studied in Chapter 3 concluding that MK-10 is and efficient acid catalysts that allows to replace the common organic acids in this reaction simplifying the reaction mixture. In order to support the rhodium catalyst in MK-10 is necessary to use cationic complexes. Then in the Chapter 4 is reported the synthesis of cationic rhodium complexes containing different mono and diphosphines. When these complexes were us