Mehanokemijska aktivacija veze C–H i halogeniranje potaknuto paladijem i usmjereno ligandom

doctoral thesis

• Title (english): Palladium-mediated ligand-directed C–H bond activation and halogenation by mechanochemistry
• Author: Dajana Barišić
• Mentor: Manda Ćurić (mentor)
• Committee member: Josip Požar (predsjednik povjerenstva)
• Committee member: Predrag Novak (član povjerenstva)
• Committee member: Davor Margetić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2022-04-27, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Izravno i selektivno uvođenje funkcionalnih skupina postignuto zamjenom inertnih veza C–H jedan je od sintetskih koraka u pripremi brojnih organskih spojeva. Ove kemijske transformacije još uvijek se pretežno oslanjaju na protokole koji uključuju upotrebu otapala, koji su često dugotrajni, zahtijevaju topljive reaktante i korištenje otrovnih otapala. U ovom su radu, kao njihova ekološki prihvatljivija alternativa, razvijeni protokoli u čvrstom stanju za aktivaciju veze C–H i halogeniranje usmjereno ligandom i katalizirano paladijevim(II) spojevima. Za ove transformacije odabrani su supstrati s donorskom skupinom koja se veže na metalni centar i dovodi ga u blizinu specifične veze C–H. Aktivacijom veze C–H nastaje reaktivna veza C–Pd koja se nakon reakcije s
N-halogensukcinimidom transformira u željenu vezu C–X. Praćenjem reakcija in situ i/ili ex situ metodama te izolacijom i karakterizacijom produkata i međuprodukata pružen je uvid u mehanizam aktivacije i halogeniranja veze C–H u čvrstom stanju i otkriven snažan učinak krutih i tekućih aditiva na prirodu i reaktivnost katalitički aktivnih vrsta Pd(II) i međuprodukata.

Abstract (english)

Direct and selective introduction of functional groups achieved by replacement of inert C–H bonds is one of the synthetic steps in the preparation of many organic compounds. These processes still rely heavily on solvent-based protocols, which are often time-consuming and require reactants solubility, and use toxic solvents. In this work, solid-state protocols for palladium-mediated ligand-directed C–H bond activation and halogenation were developed as a more environmentally friendly alternative. Substrates with donor group that binds to the metal center, positioning it near the specific C–H bond, were selected for these transformations. A reactive C–Pd bond formed during C–H bond activation transforms into the desired C–X bond upon reaction with N-halosuccinimide. Monitoring of the reactions by in situ and/or ex situ methods, as well as isolation and characterization of the products and intermediates, provided insight into the mechanism of C–H bond activation and halogenation in the solid-state and revealed a strong effect of the solid and liquid additives on the nature and reactivity of the catalytically active Pd(II) species and intermediates.

• Keywords: :aktivacija; čvrsto stanje; halogeniranje; mehanizam; mehanokemija; paladij
• Keywords (english): activation; halogenation; mechanism; mechanochemistry; palladium; solid-state
• Language: croatian
• URN:NBN: urn:nbn:hr:217:550317
• Promotion: 2022
• Project: Number: IP-2019-04-9951; Title: Mehanokemijska aktivacija i funkcionalizacija veze C–H potaknuta paladijem i usmjerena ligandom; Title: Palladium-Mediated Ligand-Directed C–H bond Activation and Functionalization by Mechanochemistry; Acronym: MECHEMFUN; Leader: Manda Ćurić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Doctoral study in chemistry; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
• Type of resource: Text
• Extent: 271 str. ; 30 cm
• File origin: Born digital
• Access conditions: Embargoed access; Embargo expiration date: 2024-04-27
• Created on: 2022-05-04 11:03:00