Razvoj metode za pripravu kiralnih višesupstituiranih ciklopentadienilnih liganada

master's thesis

• Title (english): Development of method for synthesis of chiral multisubstituted cyclopentadienyl ligands
• Author: Marko Purić
• Mentor: Nikola Topolovčan (mentor)
• Committee member: Đani Škalamera (predsjednik povjerenstva)
• Committee member: Biserka Prugovečki (član povjerenstva)
• Committee member: Aleksandra Maršavelski (član povjerenstva)
• Committee member: Željka Car (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2024-07-11, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Kompleksi prijelaznih metala s kiralnim 1,2-supstituiranim ciklopentadienilnim ligandima do sada su uspješno korišteni u brojnim stereoselektivnim transformacijama. Novija istraživanja upućuju da dodatna supstitucija prstena ciklopentadiena može povoljno utjecati na modulaciju stereoelektronskih svojstava katalitičkih džepova kompleksa. Međusobna ovisnost supstitucijskog uzorka i stereoelektronskih svojstava ukazuje na potrebu za novijim i učinkovitijim metodama sinteze takvih liganada. Ovaj rad predstavlja metodologiju za njihovu pripravu s osnovnom hipotezom da se kiralni višesupstituirani ciklopentadienilni ligandi mogu pripraviti reakcijom neterminalnog diina s Negishijevim reagensom pri čemu nastaju odgovarajući cirkonabiciklički međuprodukti. Sintetski put započinje sintezom diina i završava ciklizacijom diina s Negishijevim reagensom nakon čega slijedi reakcija unakrsnog povezivanja s alkil-dijodidom. Konačni produkt je kiralni višesupstituirani ciklopentadienilni ligand s "proširenom bočnom stijenkom" i dodanom "prednjom stijenkom".

Abstract (english)

Transition metal complexes with chiral 1,2-substituted cyclopentadienyl ligands have so far been successfully used in numerous stereoselective transformations. Recent research indicates that additional substitution of the cyclopentadiene ring can favorably influence the modulation of the stereoelectronic properties of the catalytic pockets of such complexes. The interdependence of the substitution pattern and stereoelectronic properties indicates the need for newer and more efficient methods for their synthesis. This work presents methodology for their preparation with the basic hypothesis that chiral multisubstituted cyclopentadienyl ligands can be prepared by the reaction of a non-terminal diyne with the Negishi reagent, resulting in the formation of corresponding zirconabicyclic intermediates. The synthetic route begins with the synthesis of diynes and concludes with the cyclization of diynes with the Negishi reagent, followed by a cross-coupling reaction with an alkyl diiodide. The final product is a chiral multisubstituted cyclopentadienyl ligand with an "extended sidewall" and an added "frontwall".

• Keywords: asimetrična kataliza; kiralni višesupstituirani ciklopentadienilni ligandi; BINOL-ciklopentadieni; utjecaj supstituenata na stereoselektivnost; Negishijev reagens
• Keywords (english): asymmetric catalysis; chiral multisubstituted cyclopentadienyl ligands; BINOL-cyclopentadienes; influence of substituents on stereoselectivity; Negishi reagent
• Language: croatian
• URN:NBN: urn:nbn:hr:217:200844
• Study programme: Title: Graduate university studies in chemistry; specializations in: Graduate university studies in chemistry; Course: Graduate university studies in chemistry; Study programme type: university; Study level: graduate; Academic / professional title: sveučilišni/a magistar/magistra kemije (sveučilišni/a magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Created on: 2024-07-12 11:51:37