Carboxamide substituted tetramethylcyclopentadiene - synthesis, characterisation and its iridium(iii) complex catalysed reduction of imines

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F22%3A39918913" target="_blank" >RIV/00216275:25310/22:39918913 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2022/DT/D2DT00149G" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2022/DT/D2DT00149G</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2dt00149g" target="_blank" >10.1039/d2dt00149g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Carboxamide substituted tetramethylcyclopentadiene - synthesis, characterisation and its iridium(iii) complex catalysed reduction of imines

Popis výsledku v původním jazyce

The novel dimeric iodo-iridium(iii) complex, [Ir(Cp*CONMe2)I-2](2), (Cp*CONMe2 = eta(5)-N,N-2,3,4,5-hexamethylcyclopenta-2,4-diene carboxamide) bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised and characterised. The ligand Cp*CONMe2 is synthesised as two regioisomers, however the 2-substituted isomer exists as two distinguishable conformers due to restricted rotation about the amide carbonyl carbon and the ring carbon. The relative acidities of Cp*CONMe2 and Cp* are compared by their relative rates of H/D exchange. The iridium complex of N,N-2,3,4,5-hexamethylcyclopenta-2-4-diene carboxamide [IrCp*CONMe2] and (R,R)-1,2-diphenyl-N &apos;-tosylethane-1,2-diamine ((R,R)-TsDPEN) has been evaluated in the transfer hydrogenation of imines under acidic conditions - a 5 : 2 molar ratio of formic acid : triethylamine as the hydride source for the transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline (DHIQ) and its 6,7-dimethoxy derivative in acetonitrile. A decreasing enantiomeric excess with reaction progress is attributed to different kinetic orders for formation of the two product amine enantiomers. The pseudo zero-order formation of the R-amine may be due to a pre-steady-state formation of the less stable form of the diastereomeric catalyst. By contrast, both enantiomeric amines from 1-fluorinated methyl DHIQs as substrates for reduction are formed by pseudo first-order processes.

Název v anglickém jazyce

Carboxamide substituted tetramethylcyclopentadiene - synthesis, characterisation and its iridium(iii) complex catalysed reduction of imines

Popis výsledku anglicky

The novel dimeric iodo-iridium(iii) complex, [Ir(Cp*CONMe2)I-2](2), (Cp*CONMe2 = eta(5)-N,N-2,3,4,5-hexamethylcyclopenta-2,4-diene carboxamide) bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised and characterised. The ligand Cp*CONMe2 is synthesised as two regioisomers, however the 2-substituted isomer exists as two distinguishable conformers due to restricted rotation about the amide carbonyl carbon and the ring carbon. The relative acidities of Cp*CONMe2 and Cp* are compared by their relative rates of H/D exchange. The iridium complex of N,N-2,3,4,5-hexamethylcyclopenta-2-4-diene carboxamide [IrCp*CONMe2] and (R,R)-1,2-diphenyl-N &apos;-tosylethane-1,2-diamine ((R,R)-TsDPEN) has been evaluated in the transfer hydrogenation of imines under acidic conditions - a 5 : 2 molar ratio of formic acid : triethylamine as the hydride source for the transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline (DHIQ) and its 6,7-dimethoxy derivative in acetonitrile. A decreasing enantiomeric excess with reaction progress is attributed to different kinetic orders for formation of the two product amine enantiomers. The pseudo zero-order formation of the R-amine may be due to a pre-steady-state formation of the less stable form of the diastereomeric catalyst. By contrast, both enantiomeric amines from 1-fluorinated methyl DHIQs as substrates for reduction are formed by pseudo first-order processes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

51

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

"2696–2707"

Kód UT WoS článku

000746883700001

EID výsledku v databázi Scopus

2-s2.0-85124636197