New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins

562 p.

Detalhes bibliográficos
Autor: Izquierdo Arruferia, Joseba
Formato: tesis doctoral
Fecha de publicación:2018
País:España
Recursos:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/28824
Acesso em linha:http://hdl.handle.net/10810/28824
Access Level:acceso abierto
Palavra-chave:heterocyclic compounds
organosilicon chemistry
stereochemistry and conformational analysis
compuestos heterocíclicos
química de organosilicicos
estereoquímica y análisis conformacional
id ES_a438487db376eefc78b3cada77b91e6d
oai_identifier_str oai:addi.ehu.eus:10810/28824
network_acronym_str ES
network_name_str España
repository_id_str
spelling New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoinsIzquierdo Arruferia, Josebaheterocyclic compoundsorganosilicon chemistrystereochemistry and conformational analysiscompuestos heterocíclicosquímica de organosilicicosestereoquímica y análisis conformacional562 p.The aim of this thesis has been the development of new pronucleophiles for organocatalytic reactions,leading to 2-tert-alkyl azaaryl adducts and 5,5-disubstituted hydatoins, products that are of interest inbiological and medicinal chemistry. To this end, we have developed for the first time 2-(cyanomethyl)azaarene N-oxides and 1H-imidazol-4(5H)-ones and 1H-imidazol-5(4H)-ones (Figure 1) aseasily enolizable pronucleophiles .Figure 1On one hand, 2-(cyanomethyl)azaarene N-oxides were tested in the addition to ¿-oxyenones (whose utilitywas first recognized by this group, JACS 2014, 136, 17869¿17881) using a new family ofmultifunctional squaramide-Brønsted base catalysts bearing a bulky silyl group. Reactions performedwith these catalysts gave the addition products (with quaternary stereocenters) with high yields andexcellent enantiolectivities (up to 93 % yield; up to 94% ee) (JACS 2016, 138, 3282¿3285).Scheme 2On the other hand, 1H-imidazol-4(5H)-ones and 1H-imidazol-5(4H)-ones were synthesized and evaluatedas new pronucleophiles in conjugated reactions. After acidic or basic hydrolysis, these compounds allowhighly efficient construction of 5,5-disubstituted hydantoins. Their addition to nitroolefins and vinylketones carried out with squaramide type bifunctional catalysts proceed in general with excellentstereoselectivities (up to >98:2 dr; up to >99% ee) (doi:10.1002/chem.201800506) (Scheme 3).Scheme 3In conclusion, three new pronucleophiles and two new bifunctional catalysts have been described forthe organocatalytic asymmetric formation of quaternary stereocentres. 2-Cyanomethylazaarene Noxideshave demonstrated their utility as efficient reagents for the asymmetric synthesis of ¿-quaternary o-substituted alkylazaarenes via soft enolization conditions. 1H-Imidazol-4(5H)-ones I and1H-Imidazol-5(4H)-ones II have proved to be excellent substrates for the organocatalytic Michaelreaction of enantiomerically enriched 5,5-disubstituted hydantoins.Palomo Nicolau, ClaudioLanda Alvarez, Aitor2018201820182018info:eu-repo/semantics/doctoralThesisapplication/pdfhttp://hdl.handle.net/10810/28824reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/semantics/openAccess(c)2018 JOSEBA IZQUIERDO ARRUFERIAoai:addi.ehu.eus:10810/288242026-06-18T09:23:17Z
dc.title.none.fl_str_mv New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
title New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
spellingShingle New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
Izquierdo Arruferia, Joseba
heterocyclic compounds
organosilicon chemistry
stereochemistry and conformational analysis
compuestos heterocíclicos
química de organosilicicos
estereoquímica y análisis conformacional
title_short New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
title_full New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
title_fullStr New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
title_full_unstemmed New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
title_sort New approaches to optically active 2-tert-alkyl azaaryl compounds and 5,5-disubstituted hydantoins
dc.creator.none.fl_str_mv Izquierdo Arruferia, Joseba
author Izquierdo Arruferia, Joseba
author_facet Izquierdo Arruferia, Joseba
author_role author
dc.contributor.none.fl_str_mv Palomo Nicolau, Claudio
Landa Alvarez, Aitor
dc.subject.none.fl_str_mv heterocyclic compounds
organosilicon chemistry
stereochemistry and conformational analysis
compuestos heterocíclicos
química de organosilicicos
estereoquímica y análisis conformacional
topic heterocyclic compounds
organosilicon chemistry
stereochemistry and conformational analysis
compuestos heterocíclicos
química de organosilicicos
estereoquímica y análisis conformacional
description 562 p.
publishDate 2018
dc.date.none.fl_str_mv 2018
2018
2018
2018
dc.type.none.fl_str_mv info:eu-repo/semantics/doctoralThesis
format doctoralThesis
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/28824
url http://hdl.handle.net/10810/28824
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
(c)2018 JOSEBA IZQUIERDO ARRUFERIA
eu_rights_str_mv openAccess
rights_invalid_str_mv (c)2018 JOSEBA IZQUIERDO ARRUFERIA
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869415479474388992
score 15,301603

Registos relacionados