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Identifier 000383938
Title Ετερογενής κατάλυση οργανικών αντιδράσεων από νανοσωματίδια μετάλλων προσροφημένων σε TiO2
Alternative Title Heterogeneous catalysis of organic reactions by metal nanoparticles supported on TiO2.
Author Γρυπάρης, Χάρης Δημητρίου
Thesis advisor Στρατάκης, Εμμανουήλ
Reviewer Βασιλικογιαννάκης, Γεώργιος
Hormenegildo, Garcia
Abstract In the present thesis, the cyclization of 1,6-enynes catalyzed by gold nanoparticles supported on titania (TiO2) was studied, as well as the activation of 1,2-disilanes and 1,2-silaboranes following a variety of transformations. These include hydrolysis and alcoholysis of disilanes and addition of disilanes and PhMe2SiBpin to alkynes in the presence of Au/TiO2. Mechanistic studies were performed on each reaction. The results can be summarized as follows: - Au/TiO2 catalyzes the cyclization of 1,6-enynes, providing the first heterogeneous Au protocol for this transformation. It was found that the main pathway involves a 5-exo cyclization forming stereoselectively cyclopropyl gold carbenes as intermediates. - The first example of activation of 1,2-disilanes catalyzed by Au was presented, using Au/TiO2, leading to hydrolysis and alcoholysis of symmetrical disilanes, as well as, to reduction of tert-benzylic alcohols. This methodology seems more effective than that described by a Pd(0) catalyzed protocol. - The first example of cis-disilylation of terminal alkynes from 1,2-disilanes catalyzed by Au/TiO2 was presented, as an extension of similar protocols, catalyzed by Pd and Pt, thus answering to the question: “is catalytic bis-silylation on π systems achievable through gold catalysis?” - The first example of regioselective and stereoselective cis-silaboration of terminal alkynes from PhMe2SiBpin catalyzed by Au (Au/TiO2) was presented, providing the abnormal regioselectively according to the referred in the presence of Pd(0) or Pt(0).
Language Greek
Subject 1,2-disilanes
1,2-δισιλάνια
1,6-Enynes
1,6-Ενύνια
5-exo cyclization
5-exo κυκλοποίηση
Alkynes
Disilylation
PhMe2SiBpin
PhMe2SiBpin
Regioselectivity
Silaboration
Stereoselectively
Αλκύνια
Βοριοσιλυλίωση
Δισιλυλίωση
Στερεοεκλεκτικά
Τοποεκλεκτικότητα
Issue date 2014-04-29
Collection   Faculty/Department--Faculty of Sciences and Engineering--Department of Chemistry--Doctoral theses
  Type of Work--Doctoral theses
Permanent Link https://elocus.lib.uoc.gr//dlib/2/d/c/metadata-dlib-1399021748-681048-12695.tkl Bookmark and Share
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