PHANE-TetraPHOS, a new D2 symmetric tetraphosphane based on the [2.2]paracyclophane scaffold, has been synthesized and characterized. The peculiarity of this system is the presence of four homotopic diphenylphosphane groups, exchangeable through C2 symmetry operations and consequently indistinguishable. Their spatial arrangement allows the simultaneous complexation of two metal atoms. Enantiomeric purity wasattained at tetra-phosphane oxide level by fractional crystallization of the diastereomeric adducts obtained from the racemate with enantiopure dibenzoyltartaric acids. Alkaline treatment ofdiastereomerically pure adducts followed by exhaustive PO groups reduction with HSiCl3 gave both PHANE-TetraPHOS antipodes in an enantiopure state. They were tested as rhodium ligands in the homogeneous enantioselective hydrogenation ofsome benchmark unsaturated compounds. Catalytic activity and enantiodiscrimination ability were found comparable tothose exhibited by the complexes of the parent bidentate ligand PHANEPHOS, but only half a mole of precious chiral ligand was employed.

Vaghi, L., Cirilli, R., Pierini, M., Rizzo, S., Terraneo, G., Benincori, T. (2021). PHANE‐TetraPHOS, the First D2 Symmetric Chiral Tetraphosphane. Synthesis, Metal Complexation, and Application in Homogeneous Stereoselective Hydrogenation. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2021(17 (May 7, 2021)), 2367-2374 [10.1002/ejoc.202100109].

PHANE‐TetraPHOS, the First D2 Symmetric Chiral Tetraphosphane. Synthesis, Metal Complexation, and Application in Homogeneous Stereoselective Hydrogenation

Vaghi, Luca
Primo
;
2021

Abstract

PHANE-TetraPHOS, a new D2 symmetric tetraphosphane based on the [2.2]paracyclophane scaffold, has been synthesized and characterized. The peculiarity of this system is the presence of four homotopic diphenylphosphane groups, exchangeable through C2 symmetry operations and consequently indistinguishable. Their spatial arrangement allows the simultaneous complexation of two metal atoms. Enantiomeric purity wasattained at tetra-phosphane oxide level by fractional crystallization of the diastereomeric adducts obtained from the racemate with enantiopure dibenzoyltartaric acids. Alkaline treatment ofdiastereomerically pure adducts followed by exhaustive PO groups reduction with HSiCl3 gave both PHANE-TetraPHOS antipodes in an enantiopure state. They were tested as rhodium ligands in the homogeneous enantioselective hydrogenation ofsome benchmark unsaturated compounds. Catalytic activity and enantiodiscrimination ability were found comparable tothose exhibited by the complexes of the parent bidentate ligand PHANEPHOS, but only half a mole of precious chiral ligand was employed.
Articolo in rivista - Articolo scientifico
Asymmetric catalysis; Chiral tetraphosphane; D; 2; symmetry; Homogeneous hydrogenation; Rhodium complexes;
English
6-apr-2021
2021
2021
17 (May 7, 2021)
2367
2374
open
Vaghi, L., Cirilli, R., Pierini, M., Rizzo, S., Terraneo, G., Benincori, T. (2021). PHANE‐TetraPHOS, the First D2 Symmetric Chiral Tetraphosphane. Synthesis, Metal Complexation, and Application in Homogeneous Stereoselective Hydrogenation. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2021(17 (May 7, 2021)), 2367-2374 [10.1002/ejoc.202100109].
File in questo prodotto:
File Dimensione Formato  
ejoc.202100109.pdf

accesso aperto

Descrizione: Articolo principale
Tipologia di allegato: Publisher’s Version (Version of Record, VoR)
Dimensione 1.94 MB
Formato Adobe PDF
1.94 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/314996
Citazioni
  • Scopus 3
  • ???jsp.display-item.citation.isi??? 3
Social impact