Competitive asymmetric transfer hydrogenation of 3,4-dihydroisoquinolines employing Noyori-Ikariya catalytic complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388971%3A_____%2F18%3A00501216" target="_blank" >RIV/61388971:_____/18:00501216 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1007/s11144-018-1387-z" target="_blank" >http://dx.doi.org/10.1007/s11144-018-1387-z</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1007/s11144-018-1387-z" target="_blank" >10.1007/s11144-018-1387-z</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Competitive asymmetric transfer hydrogenation of 3,4-dihydroisoquinolines employing Noyori-Ikariya catalytic complexes

Popis výsledku v původním jazyce

Competitive asymmetric transfer hydrogenation (ATH) of three differently methoxy-substituted 1-methyl-3,4-dihydroisoquinolines (1-Me-DHIQs) was carried out to examine the differences in their reactivity with six ruthenium complexes of the Noyori-Ikariya type having the general formula [Ru(II)Cl(eta(6)-arene)(N-arylsulfonyl-DPEN)] (DPEN = 1,2-diphenylethylene-1,2-diamine). The reaction kinetics of two or three substrates at once was followed in situ by H-1 NMR spectroscopy. A method originally developed for heterogeneous catalysis was used to evaluate the experimental data, providing selectivities of the catalysts to the particular substrates and affinity of these substrates to the active site. The higher reaction rate was usually connected with both higher selectivity and affinity. However, in several cases, the opposite behavior was observed, pointing to a higher selectivity towards the less reactive substrate, which can inhibit the reaction due to its higher affinity. No competitive behavior was manifested in terms of enantioselectivity. As the structure of the Noyori-Ikariya catalytic complexes is highly variable and previous structure-activity studies have often been inconclusive, the presented method may aid in the disentanglement of the complex relationships important for rational catalyst design.

Název v anglickém jazyce

Competitive asymmetric transfer hydrogenation of 3,4-dihydroisoquinolines employing Noyori-Ikariya catalytic complexes

Popis výsledku anglicky

Competitive asymmetric transfer hydrogenation (ATH) of three differently methoxy-substituted 1-methyl-3,4-dihydroisoquinolines (1-Me-DHIQs) was carried out to examine the differences in their reactivity with six ruthenium complexes of the Noyori-Ikariya type having the general formula [Ru(II)Cl(eta(6)-arene)(N-arylsulfonyl-DPEN)] (DPEN = 1,2-diphenylethylene-1,2-diamine). The reaction kinetics of two or three substrates at once was followed in situ by H-1 NMR spectroscopy. A method originally developed for heterogeneous catalysis was used to evaluate the experimental data, providing selectivities of the catalysts to the particular substrates and affinity of these substrates to the active site. The higher reaction rate was usually connected with both higher selectivity and affinity. However, in several cases, the opposite behavior was observed, pointing to a higher selectivity towards the less reactive substrate, which can inhibit the reaction due to its higher affinity. No competitive behavior was manifested in terms of enantioselectivity. As the structure of the Noyori-Ikariya catalytic complexes is highly variable and previous structure-activity studies have often been inconclusive, the presented method may aid in the disentanglement of the complex relationships important for rational catalyst design.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Reaction Kinetics Mechanism and Catalysis

ISSN

1878-5190

e-ISSN

—

Svazek periodika

124

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

10

Strana od-do

701-710

Kód UT WoS článku

000438687600016

EID výsledku v databázi Scopus

2-s2.0-85043372376