Ruthenium complexes of P-stereogenic phosphines with a heterocyclic substituent

Clavero, Pau; Grabulosa, Arnald; Rocamora, Mercè; Muller, Guillermo; Font-Bardı́a, Mercè

doi:10.1039/c6dt00995f

Cited by 19 publications

(19 citation statements)

References 87 publications

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“…The best precursor is Pd11′ (Entry 13), the cationic complex with ligand L11 . It is interesting to note that the same ligand was also the most stereoselective in transfer hydrogenation with Ru …”

Section: Resultssupporting

confidence: 90%

“…Very recently, we described a series of monophosphorus, P ‐stereogenic ligands containing a heterocyclic substituent [4‐dibenzofuryl (DBF), 4‐dibenzothiophenyl (DBT), 4‐dibenzothiophenyl (DBTO 2 ) and 1‐thianthrenyl (TA)] designed with the aim of disposing the heteroatom of the heterocycle in a suitable position allowing it to interact with the metal atom (Scheme ).…”

Section: Introductionmentioning

confidence: 79%

“…The complexation studies described here with the Pd–η 3 ‐methallyl moiety can be compared with analogous recently described studies with the Ru–η 6 ‐arene moiety . For the Ru systems it was found that both DBT‐ and TA‐based phosphanes effectively coordinated to the Ru atom in a κ 2 P , S ‐mode but the DBF‐based ligands did not.…”

Section: Resultsmentioning

confidence: 99%

“…We next moved to study of the coordinative interactions between the heterocycle and the Pd centre. Following our previous report with ruthenium, [4] we treated the neutral complexes Pd7 and Pd10 with thallium hexafluorophosphate in dichloromethane, and the solid obtained after the filtration of TlCl and removal of the solvent was analysed by NMR (Scheme 4).…”

Section: Preparation Of Cationic Pd Complexes Pd1′-13′mentioning

confidence: 99%

“…Very recently, [4] we described a series of monophosphorus, P-stereogenic ligands containing a heterocyclic substituent [4dibenzofuryl (DBF), 4-dibenzothiophenyl (DBT), 4-dibenzothiophenyl (DBTO 2 ) and 1-thianthrenyl (TA)] designed with the aim of disposing the heteroatom of the heterocycle in a suitable position allowing it to interact with the metal atom (Scheme 1). scribed in previous reports, [5,7] they were obtained by splitting dimer D with slightly more than four equivalents of phosphane in the presence of an excess of ammonium hexafluorophosphate (Scheme 3).…”

Section: Introductionmentioning

confidence: 98%

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Neutral and Cationic Palladium Complexes of P‐Stereogenic Phosphanes Bearing a Heterocyclic Substituent

et al. 2016

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The coordination chemistry of 13 optically pure P‐stereogenic diarylmonophosphanes P(Het)PhR [Het = 4‐dibenzofuranyl (DBF), 4‐dibenzothiophenyl (DBT), 4‐dibenzothiophenyl S,S‐dioxide (DBTO2) and 1‐thianthrenyl (TA); R = OMe, Me, iPr, Fc (ferrocenyl)] to Pd‐allyl moieties is described. Both neutral [PdCl(η3‐(2‐methylallyl)(κP‐P)] and cationic [Pd{η3‐(2‐methylallyl)(κP‐P)2}]PF6 complexes have been prepared. Coordination of the heteroatom of the heterocycle was only possible in the case of TA‐based phosphanes; these furnished complexes of the type [Pd{η3‐(2‐methylallyl)(κ2P,S‐P)}]PF6 after chloride abstraction with TlPF6. The crystal structure of the complex [Pd(η3‐2‐methylallyl)(κ2P,S‐PPh(OMe)(1‐TA)]PF6 is reported. The neutral Pd complexes were found to be highly active in the hydrovinylation of styrene after activation with AgBF4, except for the TA‐based phosphanes. The cationic Pd complexes were evaluated in allylic alkylation and amination with the model substrate rac‐trans‐1,3‐diphenylprop‐2‐enyl acetate (rac‐I), achieving total conversions and up to 70 % ee.

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Section: Resultssupporting

confidence: 90%

Section: Introductionmentioning

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Section: Preparation Of Cationic Pd Complexes Pd1′-13′mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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Neutral and Cationic Palladium Complexes of P‐Stereogenic Phosphanes Bearing a Heterocyclic Substituent

et al. 2016

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Diphosphorus Ligands Containing a P‐Stereogenic Phosphane and a Chiral Phosphite or Phosphorodiamidite – Evaluation in Pd‐Catalysed Asymmetric Allylic Substitution Reactions

et al. 2016

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The synthesis of 14 new optically pure C1‐symmetric phosphane–phosphinite (1–4), phosphane–phosphite (5–9) and phosphane–phosphorodiamidite (10–14) ligands is reported. The ligands were prepared through the condensation of (2‐hydroxyphenyl)phenylphosphanes PPh(2‐PhOH)R (R = Me, tBu and Ph) with chlorodiisopropylphosphane (1 and 2), chlorodiphenylphosphane (3 and 4), the chlorodioxaphosphepine derived from both enantiomers of 1,1′‐bi‐2‐naphthol (5–9) and the chlorodiazaphosphepine derived from both enantiomers of N,N′‐dimethyl‐1,1′‐binaphthyl‐2,2′‐diamine (10–14) in the presence of a base. With these ligands, cationic Pd complexes of the type [Pd(η3‐C4H7)(PP′)]PF6 (Pd1–Pd14) were obtained and characterised; the crystal structures of Pd1, Pd2 and Pd13 were obtained. In solution, the complexes are present as mixtures of two diastereomers because of the lack of symmetry of the ligand and the presence of the methallyl group. The Pd complexes catalyse the allylic alkylation with dimethyl malonate and the amination with benzylamine of the model substrate rac‐3‐acetoxy‐1,3‐diphenyl‐1‐propene (I). For the alkylation, full conversions and good enantioselectivities (up to 96 % ee with Pd14) were observed.

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Synthesis, Chiral Resolution, and Optical Properties of 2,18‐Dihydoxy‐5,10,15‐trioxa[9]helicene

et al. 2020

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Herein, we report a simple and efficient approach to synthesize a functionalized 2,18‐dimethoxy‐5,10,15‐trioxa[9]helicene. It was synthesized from simple phenol building blocks using two subsequent reactions namely oxidative coupling and dehydrative cyclization or palladium mediated cyclization. The molecular integrity of the helical core was determined by single‐crystal X‐ray diffraction and NMR techniques. Its crystal structure showed the spontaneous resolution which was attributed to the conglomerate formation of the same helical isomer via C−H⋅⋅⋅O and π⋅⋅⋅π or H⋅⋅⋅π interactions. Then, it was converted to racemic 2,18‐dihydoxy‐5,10,15‐trioxa[9]helicene. Enantiomers were separated on preparative HPLC with high optical purity (>99 % ee). Based on electronic circular dichroism, the absolute configurations of dextrorotary and levorotatory antipodes were assigned as P and M, respectively. We also studied the absorption, emission and chiroptical behavior of these helical compounds in the solution state.

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Ruthenium complexes of P-stereogenic phosphines with a heterocyclic substituent

Cited by 19 publications

References 87 publications

Neutral and Cationic Palladium Complexes of P‐Stereogenic Phosphanes Bearing a Heterocyclic Substituent

Neutral and Cationic Palladium Complexes of P‐Stereogenic Phosphanes Bearing a Heterocyclic Substituent

Diphosphorus Ligands Containing a P‐Stereogenic Phosphane and a Chiral Phosphite or Phosphorodiamidite – Evaluation in Pd‐Catalysed Asymmetric Allylic Substitution Reactions

Synthesis, Chiral Resolution, and Optical Properties of 2,18‐Dihydoxy‐5,10,15‐trioxa[9]helicene

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