Synthesis of enantiopure cyclopentanones by desymmetrization of allylic cyclobutanols

Portolani, Chiara (2020) Synthesis of enantiopure cyclopentanones by desymmetrization of allylic cyclobutanols. [Laurea magistrale], Università di Bologna, Corso di Studio in Chimica industriale [LM-DM270]
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The interest in five-membered ring molecules derives from their important application in many different fields, such as pharmaceutical and agrochemical areas. A common strategy for their formation is four-membered ring expansion, which also allows to add molecular complexity and functional handles within one single operation starting from readily available starting materials. Organocatalysis can be exploited to promote the reaction and to obtain a good enantio- and diastereoselection. This technique involves the exclusive use of organic molecules as catalysts, without resorting to metals. The aim of this work is to obtain enantiopure cyclopentanones starting from achiral allylic cyclobutanols. The reaction consists in a ring expansion promoted by the addition of a halogen to the double bond of the substrate, with formation of a haliranium ion as intermediate, followed by a semipinacol rearrangement to afford the cyclopentanone. The reaction is catalysed by a chiral phosphoric acid that, besides accelerating the rate of the reaction, transmits a specific chirality thanks to its chiral structure, following the asymmetric catalysis principles. Starting from symmetric trans-allylic cyclobutanols, the whole reaction is a desymmetrization and leads to the formation of two new stereogenic centres: a mixture of diastereoisomers is obtained, each as couple of enantiomers; the ratio between the possible configurations is determined by the relative position that the chiral catalyst and the reagent occupy during the reaction. Since the reaction is already optimized, the original aim was to study the scope: first, the synthesis of a set of allylic cyclobutanols and their relative precursors, in order to have a wider range of substrates; then, the identification of the type of substrate that undergoes the expansion, with the study of enantio- and diastereoselectivity obtained in each case. Due to the Covid-19 emergency, most of the work was developed as a bibliographic study.

Tipologia del documento
Tesi di laurea (Laurea magistrale)
Autore della tesi
Portolani, Chiara
Relatore della tesi
Correlatore della tesi
Corso di studio
Ordinamento Cds
Parole chiave
ring expansion semipinacol rearrangement enantioselectivity diastereoselectivity chiral phosphoric acid haliranium ion organocatalysis desymmetrization allylic cyclobutanol
Data di discussione della Tesi
20 Ottobre 2020

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