Assessing the role of substituents in ferrocene acylphosphines and their impact on gold-catalysed reactions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F23%3A10464671" target="_blank" >RIV/00216208:11310/23:10464671 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=2fyF3EEE_6" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=2fyF3EEE_6</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d3nj00201b" target="_blank" >10.1039/d3nj00201b</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Assessing the role of substituents in ferrocene acylphosphines and their impact on gold-catalysed reactions

Popis výsledku v původním jazyce

Substituents can be used to efficiently modify the coordination and catalytic behaviour of phosphine ligands. In this article, we analyse how substituents affect the properties of ferrocene acylphosphines FcC(O)PR2 (1a-d), where PR2 is PPh2 (1a), PCy2 (1b), PAd(2) (1c) and PCg (1d; Fc = ferrocenyl, Cy = cyclohexyl, Ad = 1-adamantyl, and PCg = 1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphaadamantane-8-yl). The (31)P-(77)Se scalar coupling constants 1J(PSe), determined for the corresponding phosphine selenides FcC(O)P(Se)R2 (2a-d), suggest that the basicity of the phosphine groups increases with the donor ability of the substituents R, as expected. Au(I) complexes [AuCl(1-κP)] (3a-d), obtained by replacing the dimethylsulfide ligand in [AuCl(SMe2)] with acylphosphines 1a-d, were tested in Au-catalysed alkyne hydration and intramolecular cyclisation of N-propargyl benzamide to yield 5-methylene-2-phenyl-4,5-dihydrooxazole. The collected results indicate that the highest reaction yields were generally obtained using catalysts derived from acylphosphines bearing the electron-donating aliphatic substituents 1b and 1c. From a wider perspective, the carbonyl moiety in the acylphosphines FcC(O)PR2 appears to lower steric crowding around the phosphorus atom (especially for compounds with bulky R substituents) and counterbalances the electron-donating effect of the ferrocenyl moiety.

Název v anglickém jazyce

Assessing the role of substituents in ferrocene acylphosphines and their impact on gold-catalysed reactions

Popis výsledku anglicky

Substituents can be used to efficiently modify the coordination and catalytic behaviour of phosphine ligands. In this article, we analyse how substituents affect the properties of ferrocene acylphosphines FcC(O)PR2 (1a-d), where PR2 is PPh2 (1a), PCy2 (1b), PAd(2) (1c) and PCg (1d; Fc = ferrocenyl, Cy = cyclohexyl, Ad = 1-adamantyl, and PCg = 1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphaadamantane-8-yl). The (31)P-(77)Se scalar coupling constants 1J(PSe), determined for the corresponding phosphine selenides FcC(O)P(Se)R2 (2a-d), suggest that the basicity of the phosphine groups increases with the donor ability of the substituents R, as expected. Au(I) complexes [AuCl(1-κP)] (3a-d), obtained by replacing the dimethylsulfide ligand in [AuCl(SMe2)] with acylphosphines 1a-d, were tested in Au-catalysed alkyne hydration and intramolecular cyclisation of N-propargyl benzamide to yield 5-methylene-2-phenyl-4,5-dihydrooxazole. The collected results indicate that the highest reaction yields were generally obtained using catalysts derived from acylphosphines bearing the electron-donating aliphatic substituents 1b and 1c. From a wider perspective, the carbonyl moiety in the acylphosphines FcC(O)PR2 appears to lower steric crowding around the phosphorus atom (especially for compounds with bulky R substituents) and counterbalances the electron-donating effect of the ferrocenyl moiety.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA19-09334S" target="_blank" >GA19-09334S: Nekonvenční ferrocenové fosfiny</a><br>

Návaznosti

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

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

New Journal of Chemistry

ISSN

1144-0546

e-ISSN

1369-9261

Svazek periodika

47

Číslo periodika v rámci svazku

9

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

11

Strana od-do

4510-4520

Kód UT WoS článku

000932668100001

EID výsledku v databázi Scopus

2-s2.0-85148422195