From Click Chemistry to catalytic cleavage of unstrained C-C bonds

Identifier:  TDX:2384

Handle: https://hdl.handle.net/20.500.11797/TDX2384

Authors:  Sau Roca, Míriam

Abstract:
This PhD thesis is based basically on synthesis of small molecules potentially useful for further investigations. Different strategies have been used to obtain them; 1) Copper free intramolecular cycloadditions between an azide and an akyne for the obtention of benzodiazepine derivatives. A wide range of triazoles fused to seven membered heterocycles rings have been obtained. Later, biological studies have been carried out. 2)a) Carbon-carbon bond cleavage of amino alcohols has been carried out with the subsequent use of them as a nucleophile together with aryl bromides to develop a cross-coupling reaction for the obtention of dibenzyl amines. A wide optimization of the reaction parameters was carried out; base, ligand, catalyst, electrophile, temperatura, and solent. b) Carbon-carbon bond cleavage of N- allyl amino alcohols has been carried out with the subsequent use of them as a nucleophile together with aryl bromides to develop a cross-coupling reaction for the obtention of beta arylated aldehydes. An important number of new amino alcohols have been synthesized and these have been subjected to the optimized reaction conditions. It has been demonstrated that this transformation is useful for a wide range of substrates (amino alcohols and aryl bromides). The resultant enamine has been alkylated with methyl vinyl ketone with good yields but poor diastereoselectivity. To finish the enantioselective version of beta functionalization of aldehydes has been developed obtaining good enantioselectivity but poor yields