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Identifier

000381418

Title

Μελέτη του μηχανισμού ενυδάτωσης αλκυνίων καταλυόμενη από σύμπλοκα χρυσού

Alternative Title

Mechanistic studies in the hydration of alkynes catalyzed by gold complexes

Author

Βελεγράκη, Γεωργία Ε

Thesis advisor

Στρατάκης, Εμμανουήλ

Reviewer

Ορφανόπουλος, Μιχαήλ
Βασιλικογιαννάκης, Γεώργιος

Abstract

In the current Thesis we studied the nature of the bonding interaction among Au(Ι or ΙΙΙ) and the C-C triple bond, in the gold-catalyzed hydration of terminal alkynes by using aryl-substituted cyclopropyl alkynes as highly sensitive probes. For comparison purposes the same hydration reaction were studies under catalysis by Ag(I), Fe(III) and Hg(II). Moreover, we present a mechanistic study in the Au(I)-catalyzed Meyer-Schuster rearrangement of internal alkynols. The results can be summarized as follows: -The Au(I or III) catalyzed activation of alkynes does not generate vinyl carbocations as intermediates as judged by the lack of allene-type rearrangement products when aryl-substituted cyclopropyl alkynes were utilized as highly sensitive probes. The Hg(II)-catalyzed activation of alkynes provides the same result as gold. - By contrast, vinyl carbocations are formed as intermediates in the interaction of alkynes with Ag(I) and Fe(III). - The Au(I) catalyzed Meyer-Schuster rearrangement of internal alkynols is a further example which shows the reluctance of a Au+-bound alkyne to undergo cyclopropyl rearrangement into an allene.

Language

Greek

Subject

Aryl-substituted cyclopropyl alkynes

Homogeneous gold catalysis

Meyer-Schuster rearrangement

Αντίδραση αναδιάταξης Meyer-Schuster

Αρυλο-υποκατεστημένα κυκλοπροπυλο-αλκύνια

Κατάλυση από σύμπλακα Au

Issue date

2013-11-15

Collection