Breaking reactivity borders: engineering stereoselective reactions with organocatalytic tools

Corti, Vasco (2019) Breaking reactivity borders: engineering stereoselective reactions with organocatalytic tools, [Dissertation thesis], Alma Mater Studiorum Università di Bologna. Dottorato di ricerca in Chimica, 31 Ciclo.
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Abstract

The research focuses of my graduate education have been dealing with two main topics: the development of stereodivergent organocatalytic processes and the development of asymmetric dual-catalytic transformations. With regard to the first topic, stereodivergent processes can be defined as the synthetic sequence that allows accessing any given stereoisomers of the same product, which bears multiple stereocentres, from the same set of starting materials. The applied strategies led to the development of the first organocatalytic asymmetric example of sulfa-Michael-reductive amination synthetic sequence to access optically active 1,5-benzothiazepines, which are attractive scaffolds in the pharmaceutical field. In addition to this, thanks to a sequential catalytic approach, we developed the stereodivergent synthesis of β,β-disubstituted-α-amino acid derivatives. This protocol gives access to all the stereoisomeric forms of the desired product bearing two contiguous chiral centres. With respect to the second topic, multicatalysis strategies have emerged as powerful tool in reaction engineering. In particular, synergistic catalysis wherein two catalysts/catalytic cycles work in concert to create new bonds has attracted a great attention. With this focus in mind, we recently started to study the catalytic asymmetric [3+2] formal cycloaddition of vinylcyclopropanes and imines promoted by a palladium based metal catalyst and a chiral phosphoric acid as organocatalysts obtaining promising results in terms of reactivity and stereoselectivity. Furthermore, during my visiting period at Aarhus university, under the supervision of Prof. Karl Anker Jørgensen, I had the chance to develop the dual catalytic asymmetric oxidative γ-coupling of α,β-unsaturated aldehydes with air as the terminal oxidant obtaining the desired enantioenriched product with excellent stereoinduction and good yield values.

Abstract
Tipologia del documento
Tesi di dottorato
Autore
Corti, Vasco
Supervisore
Co-supervisore
Dottorato di ricerca
Ciclo
31
Coordinatore
Settore disciplinare
Settore concorsuale
Parole chiave
organocatalysis, asymmetric synthesis, stereodivergent synthesis, dual catalysis
URN:NBN
Data di discussione
4 Aprile 2019
URI

Altri metadati

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