Synthesis and catalytic activity of ruthenium complexes modified with chiral racemic per- and polyfluorooxaalkanoates

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F16%3A43902741" target="_blank" >RIV/60461373:22310/16:43902741 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/16:00467331

Výsledek na webu

<a href="https://www.journals.elsevier.com/journal-of-fluorine-chemistry/" target="_blank" >https://www.journals.elsevier.com/journal-of-fluorine-chemistry/</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jfluchem.2016.09.005" target="_blank" >10.1016/j.jfluchem.2016.09.005</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis and catalytic activity of ruthenium complexes modified with chiral racemic per- and polyfluorooxaalkanoates

Popis výsledku v původním jazyce

Silver salts of racemic 2H-perfluoro(3-oxahexanoic) (3a), perfluoro(2-methyl-3-oxahexanoic) (3b) and 2,3,3,3-tetrafluoro-2-methoxypropanoic acid (3c) gave with Hoveyda-Grubbs 2nd generation catalyst 4 or its bis(polyfiuoroalkylated) analogue 5 the corresponding bis(polyfluoroacylated) ruthenium complexes 1a-1c or 2a, 2b as mixtures of three diastereoisomers. Their catalytic activity in model ring-closing metathesis (RCM) reactions decreased in the order 1b-2b > 1a-2a > 1c due to increased steric hindrance around the catalytic centre in complexes 1a, 1c and 2a, as well as due to lower acidity of acid 3c resulting in lower electrophilicity of the complex 1c. Thus, the complexes 1b and 2b displayed high activity in RCM of bis-unsaturated malonates forming disubstituted (RCM2) or trisubstituted (RCM3) double bond and were even significantly active in the formation of tetrasubstituted bond (RCM4), while complexes 1a, 1c were active in RCM2 but inactive in RCM3. Moreover, the yield of RCM2 catalyzed with complex is was rather low.

Název v anglickém jazyce

Synthesis and catalytic activity of ruthenium complexes modified with chiral racemic per- and polyfluorooxaalkanoates

Popis výsledku anglicky

Silver salts of racemic 2H-perfluoro(3-oxahexanoic) (3a), perfluoro(2-methyl-3-oxahexanoic) (3b) and 2,3,3,3-tetrafluoro-2-methoxypropanoic acid (3c) gave with Hoveyda-Grubbs 2nd generation catalyst 4 or its bis(polyfiuoroalkylated) analogue 5 the corresponding bis(polyfluoroacylated) ruthenium complexes 1a-1c or 2a, 2b as mixtures of three diastereoisomers. Their catalytic activity in model ring-closing metathesis (RCM) reactions decreased in the order 1b-2b > 1a-2a > 1c due to increased steric hindrance around the catalytic centre in complexes 1a, 1c and 2a, as well as due to lower acidity of acid 3c resulting in lower electrophilicity of the complex 1c. Thus, the complexes 1b and 2b displayed high activity in RCM of bis-unsaturated malonates forming disubstituted (RCM2) or trisubstituted (RCM3) double bond and were even significantly active in the formation of tetrasubstituted bond (RCM4), while complexes 1a, 1c were active in RCM2 but inactive in RCM3. Moreover, the yield of RCM2 catalyzed with complex is was rather low.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GAP207%2F10%2F1533" target="_blank" >GAP207/10/1533: Fluorové karbeny, komplexy a iontové kapaliny na bázi perfluorpolyethery substituovaných imidazoliových solí a jejich aplikace</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Journal of Fluorine Chemistry

ISSN

0022-1139

e-ISSN

—

Svazek periodika

191

Číslo periodika v rámci svazku

Listopad

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

9

Strana od-do

14-22

Kód UT WoS článku

000388058300002

EID výsledku v databázi Scopus

2-s2.0-84987920184