Synthesis of a Polar Phosphinoferrocene Amidosulfonate Ligand and Its Application in Pd-Catalyzed Cross-Coupling Reactions of Aromatic Boronic Acids and Acyl Chlorides in an Aqueous Medium

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F16%3A10328032" target="_blank" >RIV/00216208:11310/16:10328032 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.organomet.6b00600" target="_blank" >http://dx.doi.org/10.1021/acs.organomet.6b00600</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.6b00600" target="_blank" >10.1021/acs.organomet.6b00600</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis of a Polar Phosphinoferrocene Amidosulfonate Ligand and Its Application in Pd-Catalyzed Cross-Coupling Reactions of Aromatic Boronic Acids and Acyl Chlorides in an Aqueous Medium

Popis výsledku v původním jazyce

The reaction of [1'-(diphenylphosphino)ferrocenyl]methylamine (1), generated in situ from its hydrochloride and triethylamine, with 2-sulfobenzoic anhydride afforded an anionic phosphino-amide, which was isolated as a triethylammonium salt, Ph2PfcCH2NHCOC6H4SO3(HNEt3) (2; fc = ferrocene-1,1'-diyl). A similar reaction of 1 with phthalic anhydride only furnished the salt (Ph2PfcCH2NH3)[C6H4CO2H(CO2)]. When it was reacted with [PdCl2(MeCN)(2)] and [(LPd)-Pd-NC(mu-Cl)](2) (L(NC) = 2-[(dimethylamino-kappaN)methyl]phenyl-kappaC-1), compound 2 gave rise to the bisphosphine complex [PdCl2(2-kappa P)2] and the bridge-cleavage product [L(NC)PdCl(2-kappa P)], respectively. An analogue of the latter complex containing 2'-amino-[1,1'-biphenyl]-2-yl-kappaN-2,C-2 as the auxiliary chelating ligand, compound 8, was prepared in a similar manner from 2 and the respective Pd precursor. Finally, the reaction of 2 with [L(NC)Pd(acac)] proceeded with the replacement of the acetylacetonate ligand (acac), affording a dipalladium complex featuring two phosphinosulfonate anions as the O,P-bridges, [L(NC)Pd(mu(P,O)-Ph2PfcCH2NHCOC6H4SO3)](2), which was structurally characterized by single-crystal X-ray diffraction analysis. All of these Pd(II) complexes, especially compound 8, formed active catalysts for Pd-mediated cross-coupling of aromatic boronic acids with benzoyl chlorides to produce substituted benzophenones in toluene (benzene) water biphasic mixtures. This particular coupling reaction was employed during the preparation of 4'-chloro-4-hydroxybenzophenone, which was in turn converted to fenofibrate, a generic drug widely used to reduce cholesterol levels in blood.

Název v anglickém jazyce

Synthesis of a Polar Phosphinoferrocene Amidosulfonate Ligand and Its Application in Pd-Catalyzed Cross-Coupling Reactions of Aromatic Boronic Acids and Acyl Chlorides in an Aqueous Medium

Popis výsledku anglicky

The reaction of [1'-(diphenylphosphino)ferrocenyl]methylamine (1), generated in situ from its hydrochloride and triethylamine, with 2-sulfobenzoic anhydride afforded an anionic phosphino-amide, which was isolated as a triethylammonium salt, Ph2PfcCH2NHCOC6H4SO3(HNEt3) (2; fc = ferrocene-1,1'-diyl). A similar reaction of 1 with phthalic anhydride only furnished the salt (Ph2PfcCH2NH3)[C6H4CO2H(CO2)]. When it was reacted with [PdCl2(MeCN)(2)] and [(LPd)-Pd-NC(mu-Cl)](2) (L(NC) = 2-[(dimethylamino-kappaN)methyl]phenyl-kappaC-1), compound 2 gave rise to the bisphosphine complex [PdCl2(2-kappa P)2] and the bridge-cleavage product [L(NC)PdCl(2-kappa P)], respectively. An analogue of the latter complex containing 2'-amino-[1,1'-biphenyl]-2-yl-kappaN-2,C-2 as the auxiliary chelating ligand, compound 8, was prepared in a similar manner from 2 and the respective Pd precursor. Finally, the reaction of 2 with [L(NC)Pd(acac)] proceeded with the replacement of the acetylacetonate ligand (acac), affording a dipalladium complex featuring two phosphinosulfonate anions as the O,P-bridges, [L(NC)Pd(mu(P,O)-Ph2PfcCH2NHCOC6H4SO3)](2), which was structurally characterized by single-crystal X-ray diffraction analysis. All of these Pd(II) complexes, especially compound 8, formed active catalysts for Pd-mediated cross-coupling of aromatic boronic acids with benzoyl chlorides to produce substituted benzophenones in toluene (benzene) water biphasic mixtures. This particular coupling reaction was employed during the preparation of 4'-chloro-4-hydroxybenzophenone, which was in turn converted to fenofibrate, a generic drug widely used to reduce cholesterol levels in blood.

Druh

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

CEP obor

CA - Anorganická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GA13-08890S" target="_blank" >GA13-08890S: Polární ferrocenové amidofosfinové ligandy pro katalytické aplikace</a><br>

Návaznosti

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

Rok uplatnění

2016

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

35

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

3378-3387

Kód UT WoS článku

000385209400016

EID výsledku v databázi Scopus

2-s2.0-84991203749