doktorska disertacija
Bruno Aleksander Martek (Author), Janez Košmrlj (Mentor), Jernej Iskra (Thesis defence commission member), Marjan Jereb (Thesis defence commission member), Zdenko Časar (Thesis defence commission member)

Abstract

V doktorskem delu smo predstavili nova spoznanja, poti in metode Sonogashirovega alkiniliranja (hetero)aril bromidov in kloridov pri sobni temperaturi, brez bakra kot ko-katalizatorja. S sočasno uporabo dveh različnih paladijevih predkatalizatorjev, pri čemer je eden omogočal oksidativno adicijo (hetero)aril bromidov, drugi pa aktivacijo terminalnih acetilenov, smo razvili katalitski sistem, ki temelji na Pd–Pd transmetalaciji. Z omenjenim katalitskim sistemom smo uspešno sintetizirali serijo alkil, aril in heteroaril substituiranih alkinov pri sobni temperaturi brez uporabe bakra. Neodvisno smo pripravili dva ključna intermediata, oksidativni adukt in paladijev acetilid, ter z njima ponazorili korak transmetalacije, ki je vodila do nastanka želenih produktov. S tandemom Pd–Pd smo prav tako uspešno pripravili sintezni intermediat zdravilne učinkovine (API) in izvedli reakcijo na več-gramski skali, pri čemer smo uporabili zgolj 0.125 mol % celokupnega paladija. Poleg tega smo razvili še dva katalitska sistema za alkiniliranje (hetero)aril bromidov in kloridov pri sobni temperaturi. Sistem (PhCN)2PdCl2/JohnPhos nam je omogočal pretvorbe aktiviranih in deaktiviranih (hetero)aril bromidov ob uporabi zgolj stehiometrijske količine aril in alkil acetilenov pri sobni temperaturi. Sistem je bil tudi uporabljen na več-gramski skali, kjer smo za dosego želenega rezultata potrebovali zgolj 0.0125 mol % paladija. S sistemom PdCl2/XPhos pa smo uspešno pretvorili slabše reaktivne aril kloride v pripadajoče alkinilirane produkte ter s tem predstavili do sedaj prvi katalitski sistem zmožen alkiniliranja aril kloridov brez bakra pri sobni temperaturi oziroma pri temperaturi 60°C.

Keywords

reakcije spajanja;Sonogashirova reakcija;alkiniliranje;transmetalacija;mehanizem;paladij;paladijevi fosfinski kompleksi;paladijevi tiosemikarbazonatni kompleksi;aril halidi;doktorske disertacije;

Data

Language: Slovenian
Year of publishing:
Typology: 2.08 - Doctoral Dissertation
Organization: UL FKKT - Faculty of Chemistry and Chemical Technology
Publisher: [B. A. Martek]
UDC: 544.47:546.98:547(043.3)
COBISS: 32160515 Link will open in a new window
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Downloads: 224
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Other data

Secondary language: English
Secondary title: Dual role of palladium catalyst in alkynylation of aryl halides
Secondary abstract: This thesis is aimed to introduce novel insights, systems and methods in Sonogashira alkynylation of (hetero)aryl bromides and chlorides at room temperature in the absence of copper co-catalyst. By simultaneous introduction of two different palladium pre-catalysts, one tuned to promote oxidative addition of (hetero)aryl bromides, and the other tuned to activate terminal acetylenes, novel catalytic system was developed based on effective Pd–Pd transmetallation. Herein described Pd–Pd system was used in the synthesis of alkyl, aryl and heteroaryl substituted alkynes at room temperature without any copper additives. Two key intermediates, oxidative addition adduct and palladium acetylide, were prepared independently, and used in the transmetallation reaction to produce desired cross-coupled products. Pd–Pd tandem was also used in the preparation of synthetic intermediate of active pharmaceutical ingredient (API),and in a multi-gram scale synthesis with as low as 0.125 mol % of total palladium loading. In addition, two other catalytic systems for alkynylation of (hetero)aryl halides at room temperature have been developed. The system (PhCN)2PdCl2/JohnPhos was able to cross-couple activated and deactivated (hetero)aryl bromides with only stoichiometric amounts of aryl and alkyl acetylenes at room temperature. Furthermore, it was also used on a multi-gram scale synthesis where only 0.0125 mol % of palladium was needed to achieve the desired results. The system PdCl2/XPhos enabled couplings of less reactive aryl chlorides and alkynes into desired alkynylation products and represents the first catalytic system capable of alkynylation of aryl chlorides with no copper additives at room temperature or at 60 °C.
Secondary keywords: palladium;cross-coupling;Sonogashira reaction;transmetallation;mechanism;
Type (COBISS): Doctoral dissertation
Study programme: 1000381
Embargo end date (OpenAIRE): 1970-01-01
Thesis comment: Univ. v Ljubljani, Fak. za kemijo in kemijsko tehnologijo
Pages: XVII, 134 str.
ID: 12050936