Synthesis, Coordination, and Catalytic Use of 1'- (Diphenylphosphino)ferrocene-1-sulfonate Anion

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10376030" target="_blank" >RIV/00216208:11310/18:10376030 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/acs.organomet.8b00178" target="_blank" >https://doi.org/10.1021/acs.organomet.8b00178</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.8b00178" target="_blank" >10.1021/acs.organomet.8b00178</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis, Coordination, and Catalytic Use of 1'- (Diphenylphosphino)ferrocene-1-sulfonate Anion

Popis výsledku v původním jazyce

Sulfonation of (diphenylphosphinothioyl)ferrocene (1) with chlorosulfonic acid in acetic anhydride affords the crude sulfonic acid Ph2P(S)fcSO(3)H (2; fc = ferrocene-1,1&apos;-diyl), which can be efficiently purified and isolated after conversion to Ph2P(S)fcSO(3)(HNEt3) (3). Methyl triflate/P(NMe2)(3) can be used to convert compound 3 to the stable sulfonate salt Ph(2)PfcSO(3) (HNEt3) (4) and Ph2P(Me)fcSO(3) (5) as a minor, zwitterionic byproduct. Alternatively, compound 4 can be prepared by lithiation of 1&apos;-(diphenylphosphino)-1-bromoferrocene (6; Ph(2)PfcBr) and trapping of the lithiated intermediate with SO3 . NMe3. Reactions of [(L-NC)PdX](2)and [(L-SC)PdX](2), where X = Cl, AcO, L-NC = 2-[(dimethylamino-kappa N)methyl]phenyl-kappa C-1, and L-SC = 2[(methylthio-kappa S)methyl]phenyl-kappa C-1, with 4 uniformly produced the bis-chelate complexes [(L-NC)Pd(Ph(2)PfcSO(3)-kappa O-2,P)] (7) and [(L-SC)Pd(Ph(2)PfcSO(3)-kappa O-2,P)] (8), respectively. The reaction of [PdCl2(MeCN)(2)] with 4 afforded the bis(phosphine) complex trans-(Et3NH)(2)[PdCl2 (Ph(2)PfcSO(3)-kappa P)(2)] (9). Complexes 7-9 were used as defined catalyst precursors for the Suzuki- Miyaura cross-coupling of boronic acids with acyl chlorides to give ketones. Reactions of aromatic substrates in the presence of Na3PO4 and 9, the base and Pd source that showed the best performance, in a toluene/water biphasic system provided the coupling products in good yields; however, aliphatic substrates typically resulted in poor conversions. Extensive tests of the reaction scope revealed that the transposition of the substituents between the reaction partners can have a substantial effect on the yield of the coupling product in otherwise complementary reactions, which highlights the importance of the judicious choice of starting materials for this particular reaction.

Název v anglickém jazyce

Synthesis, Coordination, and Catalytic Use of 1'- (Diphenylphosphino)ferrocene-1-sulfonate Anion

Popis výsledku anglicky

Sulfonation of (diphenylphosphinothioyl)ferrocene (1) with chlorosulfonic acid in acetic anhydride affords the crude sulfonic acid Ph2P(S)fcSO(3)H (2; fc = ferrocene-1,1&apos;-diyl), which can be efficiently purified and isolated after conversion to Ph2P(S)fcSO(3)(HNEt3) (3). Methyl triflate/P(NMe2)(3) can be used to convert compound 3 to the stable sulfonate salt Ph(2)PfcSO(3) (HNEt3) (4) and Ph2P(Me)fcSO(3) (5) as a minor, zwitterionic byproduct. Alternatively, compound 4 can be prepared by lithiation of 1&apos;-(diphenylphosphino)-1-bromoferrocene (6; Ph(2)PfcBr) and trapping of the lithiated intermediate with SO3 . NMe3. Reactions of [(L-NC)PdX](2)and [(L-SC)PdX](2), where X = Cl, AcO, L-NC = 2-[(dimethylamino-kappa N)methyl]phenyl-kappa C-1, and L-SC = 2[(methylthio-kappa S)methyl]phenyl-kappa C-1, with 4 uniformly produced the bis-chelate complexes [(L-NC)Pd(Ph(2)PfcSO(3)-kappa O-2,P)] (7) and [(L-SC)Pd(Ph(2)PfcSO(3)-kappa O-2,P)] (8), respectively. The reaction of [PdCl2(MeCN)(2)] with 4 afforded the bis(phosphine) complex trans-(Et3NH)(2)[PdCl2 (Ph(2)PfcSO(3)-kappa P)(2)] (9). Complexes 7-9 were used as defined catalyst precursors for the Suzuki- Miyaura cross-coupling of boronic acids with acyl chlorides to give ketones. Reactions of aromatic substrates in the presence of Na3PO4 and 9, the base and Pd source that showed the best performance, in a toluene/water biphasic system provided the coupling products in good yields; however, aliphatic substrates typically resulted in poor conversions. Extensive tests of the reaction scope revealed that the transposition of the substituents between the reaction partners can have a substantial effect on the yield of the coupling product in otherwise complementary reactions, which highlights the importance of the judicious choice of starting materials for this particular reaction.

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

2018

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

37

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

1615-1626

Kód UT WoS článku

000433635600012

EID výsledku v databázi Scopus

2-s2.0-85048110168