Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F21%3A10430080" target="_blank" >RIV/00216208:11310/21:10430080 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=bzGxcbGi0i" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=bzGxcbGi0i</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.1c00244" target="_blank" >10.1021/acs.organomet.1c00244</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone

Popis výsledku v původním jazyce

Anionic phosphinoferrocene amidosulfonates bearing sterically demanding tert-butyl substituents in positions 3 and 3&apos; of the ferrocene scaffold, viz. rac-(Et3NH)[Fe(η(5)-tBuC5H3PR2)-(η(5)-tBuC5H3C(O)NHCH2SO3)] (R = phenyl, cyclohexyl), were synthesized by amidation of the corresponding phosphinocarboxylic acids, [Fe(η(5)-tBuC5H3PR2)(η(5)-tBuC5H3CO2H)]. These ditopic polar phosphinoferrocenes and their non-tert-butylated analogues have been used as ligands to prepare zwitterionic (η(3)-ally) palladium(II) complexes [Pd(η(3)-C3H5){Fe(η(5)-R&apos;C5H3PR2)(η(5)-R&apos;C5H3C(O)NHCH2SO3)}] (R&apos; = H, tBu; R = Ph, Cy). Depending on the isolation procedure and crystallization conditions, some complexes were isolated in two isomeric forms which differed in the coordination of the amidosulfonate pendant group, where either amide or sulfonated oxygen ligated the Pd(II) center. The preference for coordination of the amide or sulfonate oxygen atoms has been explained by the interplay of electrostatic and solvation effects and further supported by DFT calculations. The (η(3)-ally)Pd-II complexes have been applied as defined precatalysts for Pd-catalyzed C-H arylation of an unprotected indole with aryl iodides in polar solvents. Under the optimized reaction conditions at 100 degrees C in water, C2-arylation proceeded selectively with various aryl iodides to produce the respective 2-arylindoles in acceptable yields at a low catalyst loading (1 mol % Pd) and in the absence of any phase transfer agent. The catalyst possessing tert-butyl groups at the ferrocene core and an electron-rich dicyclohexylphosphino group exhibited the best catalytic performance.

Název v anglickém jazyce

Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone

Popis výsledku anglicky

Anionic phosphinoferrocene amidosulfonates bearing sterically demanding tert-butyl substituents in positions 3 and 3&apos; of the ferrocene scaffold, viz. rac-(Et3NH)[Fe(η(5)-tBuC5H3PR2)-(η(5)-tBuC5H3C(O)NHCH2SO3)] (R = phenyl, cyclohexyl), were synthesized by amidation of the corresponding phosphinocarboxylic acids, [Fe(η(5)-tBuC5H3PR2)(η(5)-tBuC5H3CO2H)]. These ditopic polar phosphinoferrocenes and their non-tert-butylated analogues have been used as ligands to prepare zwitterionic (η(3)-ally) palladium(II) complexes [Pd(η(3)-C3H5){Fe(η(5)-R&apos;C5H3PR2)(η(5)-R&apos;C5H3C(O)NHCH2SO3)}] (R&apos; = H, tBu; R = Ph, Cy). Depending on the isolation procedure and crystallization conditions, some complexes were isolated in two isomeric forms which differed in the coordination of the amidosulfonate pendant group, where either amide or sulfonated oxygen ligated the Pd(II) center. The preference for coordination of the amide or sulfonate oxygen atoms has been explained by the interplay of electrostatic and solvation effects and further supported by DFT calculations. The (η(3)-ally)Pd-II complexes have been applied as defined precatalysts for Pd-catalyzed C-H arylation of an unprotected indole with aryl iodides in polar solvents. Under the optimized reaction conditions at 100 degrees C in water, C2-arylation proceeded selectively with various aryl iodides to produce the respective 2-arylindoles in acceptable yields at a low catalyst loading (1 mol % Pd) and in the absence of any phase transfer agent. The catalyst possessing tert-butyl groups at the ferrocene core and an electron-rich dicyclohexylphosphino group exhibited the best catalytic performance.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

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

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

—

Svazek periodika

40

Číslo periodika v rámci svazku

12

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

1934-1944

Kód UT WoS článku

000669544500018

EID výsledku v databázi Scopus

2-s2.0-85108561399