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doctoral thesis
Primjena posredne indukcije kiralnosti u asimetričnoj katalizi
enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina
Zagreb: University of Zagreb, Faculty of Science, 2014. urn:nbn:hr:217:372173
Kokan, Zoran
University of Zagreb
Faculty of Science
Department of Chemistry

Institutional repository: Repository of the Faculty of Science

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Kokan, Z. (2014). Primjena posredne indukcije kiralnosti u asimetričnoj katalizi : enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina (Doctoral thesis). Zagreb: University of Zagreb, Faculty of Science. Retrieved from https://urn.nsk.hr/urn:nbn:hr:217:372173

Kokan, Zoran. "Primjena posredne indukcije kiralnosti u asimetričnoj katalizi : enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina." Doctoral thesis, University of Zagreb, Faculty of Science, 2014. https://urn.nsk.hr/urn:nbn:hr:217:372173

Kokan, Zoran. "Primjena posredne indukcije kiralnosti u asimetričnoj katalizi : enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina." Doctoral thesis, University of Zagreb, Faculty of Science, 2014. https://urn.nsk.hr/urn:nbn:hr:217:372173

Kokan, Z. (2014). 'Primjena posredne indukcije kiralnosti u asimetričnoj katalizi : enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina', Doctoral thesis, University of Zagreb, Faculty of Science, accessed 23 December 2024, https://urn.nsk.hr/urn:nbn:hr:217:372173

Kokan Z. Primjena posredne indukcije kiralnosti u asimetričnoj katalizi : enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina [Doctoral thesis]. Zagreb: University of Zagreb, Faculty of Science; 2014 [cited 2024 December 23] Available at: https://urn.nsk.hr/urn:nbn:hr:217:372173

Z. Kokan, "Primjena posredne indukcije kiralnosti u asimetričnoj katalizi : enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina", Doctoral thesis, University of Zagreb, Faculty of Science, Zagreb, 2014. Available at: https://urn.nsk.hr/urn:nbn:hr:217:372173

Metadata
TitlePrimjena posredne indukcije kiralnosti u asimetričnoj katalizi : enantioselektivno hidrogeniranje komplesima rodija s biokonjugatima trifenilfosfina i kiralnih aminokiselina
Title (english)Application of backdoor induction of chirality in asymmetric catalysis : enantioselective hydrogenation with rhodium complexes of triphenylphosphine amino acid bioconjugates
AuthorZoran Kokan
MBZ: 326816
MentorSrećko Kirin (mentor)
Committee memberInes Primožič (predsjednik povjerenstva)
Committee memberSrećko Kirin (član povjerenstva)
Committee memberIvo Piantanida (član povjerenstva)
MBZ: 202026
Committee memberMarina Cindrić (član povjerenstva)
GranterUniversity of Zagreb
Faculty of Science
(Department of Chemistry)
Zagreb
Defense date and country2014-06-27, Croatia
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Universal decimal classification
(UDC)		54 - Chemistry. Crystallography. Mineralogy
Abstract
U okviru ovog rada pripravljena su ukupno 73 nova liganda derivata trifenilfosfina s aminokiselinama, kraćim peptidima i/ili aminima. Ligandi su podijeljeni u tri skupine (A, B i C) obzirom na supstituciju fenilnog prstena fosfina i dentatnost, a njihovi in situ pripravljeni kompleksi s Rh(I) ispitani su kao homogeni katalizatori u reakcijama enantioselektivnog hidrogeniranja dvaju modelnih supstrata, metil-2-acetamidoprop-2-enoata (S1) i metil-(Z)-2-acetamido-3-fenilprop-2-enoata (S2). Kiralna informacija aminokiselina udaljena je od prokiralnog metala, a prenosi se "posrednom indukcijom" putem vodikovih veza. Postignuti maksimalni enantiomerni višak (ee) iznosi ee(R) = 68%, ee(S) = 84% i ee(R) = 81% upotrebom monodentatnih A, B, odnosno bidentatnih C liganda. Pripravljeni su Pd(II) i Pt(II) kompleksi s A i B u svrhu ispitivanja interakcija među ligandima. Priređeni ligandi i njihovi metalni kompleksi okarakterizirani su različitim analitičkim metodama (1H, 13C, 31P NMR, COSY, NOESY, ESI-MS, MALDI-TOF HRMS, CD i difrakcija X-zraka na jediničnom kristalu), a stereokemija produkata reakcije hidrogeniranja objašnjena je stereokemijskom analizom i DFT izračunima.
Abstract (english)
Within this thesis, a total of 73 new ligands based on triphenylphosphine derivatives with aminoacids, short peptides and/or amines, were synthesized. The ligands were divided into three categories (A, B, and C) by the phosphine phenyl ring substitution and denticity. Their in situ prepared Rh(I) complexes were tested as catalysts in the enantioselective hydrogenation of model substrates, methyl-2-acetamidoprop-2-enoate (S1) and methyl-(Z)-2-acetamido-3-phenylprop-2-enoate (S2). Chiral information from distant amino acids is transmitted to the prochiral metal through "backdoor induction" via hydrogen bonding. The obtained maximal enantiomeric excess (ee) is ee(R) = 68 %, ee(S) = 84 % and ee(R) = 81 % using monodentate A, B, and bidentate C ligands, respectively. Pd(II) and Pt(II) complexes of A and B were synthesized as model compounds for examination of ligand interactions. The ligands and their metal complexes were characterized with different analytical methods (1H, 13C, 31P NMR, COSY, NOESY, ESI-MS, MALDI-TOF HRMS, CD, and single crystal X-ray diffraction). The stereochemistry of the hydrogenation products was explained using stereochemical analysis and DFT calculations.
Keywords
Keywords (english)
Languagecroatian
URN:NBNurn:nbn:hr:217:372173
Study programmeTitle: 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 resourceText
Extent125 str. ; 30 cm
File originBorn digital
Access conditionsOpen access
Terms of useLicence In copyright icon
Created on2017-02-14 16:51:03