Helicenes as Chirality-Inducing Groups in Transition-Metal Catalysis: The First Helically Chiral Olefin Metathesis Catalyst

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F18%3A00492362" target="_blank" >RIV/61388963:_____/18:00492362 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/chem.201802786" target="_blank" >http://dx.doi.org/10.1002/chem.201802786</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201802786" target="_blank" >10.1002/chem.201802786</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Helicenes as Chirality-Inducing Groups in Transition-Metal Catalysis: The First Helically Chiral Olefin Metathesis Catalyst

Popis výsledku v původním jazyce

Helical chirality is a novel enantioselectivity-inducing property in transition-metal-catalyzed transformations. The principle is illustrated herein for the example of asymmetric olefin metathesis. This work reports the synthesis of the first helically chiral Ru-NHC alkylidene complex from an aminohelicene-derived imidazolium salt, which was ligated to the first generation Hoveyda-Grubbs catalyst. Kinetic data were acquired for benchmark test reactions and compared to an achiral catalyst. The helically chiral Ru-catalyst was evaluated in asymmetric ring-closing metathesis (RCM) and ring-opening metathesis-cross-metathesis (ROM/CM) reactions, which proceeded with promising levels of enantioselectivity. Extensive NMR-spectroscopic investigations and a DFT geometry optimization were performed. These results led to a topographic steric map and calculation of percent-buried-volume values for each quadrant around the metal center.

Název v anglickém jazyce

Helicenes as Chirality-Inducing Groups in Transition-Metal Catalysis: The First Helically Chiral Olefin Metathesis Catalyst

Popis výsledku anglicky

Helical chirality is a novel enantioselectivity-inducing property in transition-metal-catalyzed transformations. The principle is illustrated herein for the example of asymmetric olefin metathesis. This work reports the synthesis of the first helically chiral Ru-NHC alkylidene complex from an aminohelicene-derived imidazolium salt, which was ligated to the first generation Hoveyda-Grubbs catalyst. Kinetic data were acquired for benchmark test reactions and compared to an achiral catalyst. The helically chiral Ru-catalyst was evaluated in asymmetric ring-closing metathesis (RCM) and ring-opening metathesis-cross-metathesis (ROM/CM) reactions, which proceeded with promising levels of enantioselectivity. Extensive NMR-spectroscopic investigations and a DFT geometry optimization were performed. These results led to a topographic steric map and calculation of percent-buried-volume values for each quadrant around the metal center.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA16-08294S" target="_blank" >GA16-08294S: Rozsáhlé neplanárních aromatické systémy: vývoj nových funkčních materiálů</a><br>

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

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

—

Svazek periodika

24

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

5

Strana od-do

10994-10998

Kód UT WoS článku

000440547400013

EID výsledku v databázi Scopus

2-s2.0-85050496188