Stereoselektivna priprava β,β-diaril-ketona s β-tetrasupstituiranim stereogenim centrom

doctoral thesis

• Title (english): Stereoselective synthesis of β,β-diaryl ketones with β-tetrasubstituted stereogenic center
• Author: Mateja Matišić
• Mentor: Matija Gredičak (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Željka Soldin (član povjerenstva)
• Committee member: Irena Dokli (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2022-07-15, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Metodologije priprave kiralnih β,β-diaril ketona temelje se uglavnom na arilacijama 1,4-
nezasićenih ketona u prisutnosti kiralnih kompleksa prijelaznih metala kao katalizatora. Iako u
većini slučajeva generiraju tercijarni centar kiralnosti na β-ugljikovom atomu, u literaturi
postoji nekoliko primjera gdje je moguće pripraviti tetrasupstituirani stereocentar na tom
ugljikovom atomu.
U sklopu ove disertacije razvijena je organokatalitička metodologija stereoselektivne priprave
izoindolinonskih derivata β,β-diaril ketona s jednim kvaternim, odnosno dva vicinalna
stereogena centra u prinosima 35‒98 % s visokom enantioselektivnošću (e.r. = 60:40 ‒ >99:1).
Na dobivenim su produktima uspješno provedene izabrane transformacijske reakcije bez
gubitka optičke čistoće.

Abstract (english)

Methodologies for the enantioselective synthesis of chiral β,β-diaryl ketones are mainly based
on the transition metal-catalyzed arylations of 1,4-unsaturated ketones. Most strategies for
accessing these compounds yield products with tertiary stereocenters, however, there are
several examples in the literature for the contruction of a tetrasubstituted (gem)-diarylalkyl
center of chirality.
Within this dissertation, an organocatalytic methodology for the stereoselective preparation of
isoindolinone-derived β,β-diaryl ketones with one quaternary, and two vicinal stereogenic
centers is developed. Products were prepared in 35‒98% yields with high enantioselectivity
(e.r. = 60:40 ‒ 99:1). Obtained products successfully underwent postmodification reactions
without loss of optical purity.

• Keywords: β; β-diarilketoni; enantioselektivnost; izoindolinoni; organokataliza; stereoselektivna sinteza
• Keywords (english): β; β-diaril-ketones; chiral phosphoric acids; enantioselectivity; isoindolinones; organocatalysis; stereoselective synthesis
• Language: croatian
• URN:NBN: urn:nbn:hr:217:161509
• Promotion: 2022
• Project: Number: IP-2018-01-4053; Title: Nove strategije za pripravu tetrasupstituiranih kiralnih centara: asimetrične katalitičke reakcije usmjerene protuanionom; Acronym: NSYNC-ACDC; Leader: Matija Gredičak; 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: 151 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2022-10-03 16:46:45