Novel enantiomerically pure tetramethylbithiophene diphosphine oxides (tetraMe-BITIOPO) featuring differently substituted aromatic rings at the phosphorous atoms were synthesized, fully characterized and isolated in enantiomerically pure form. The new Lewis bases were tested as organocatalysts in two different reactions involving trichlorosilyl compounds. The introduction of electron donating substituents on the aromatic rings connected to the phosphine oxide groups positively affected the chemical and stereochemical catalytic efficiency of these ligands. The new catalysts were able to promote the allylation of aldehydes with allyltrichlorosilane in up to 76% yield and up to 86% enantiomeric excess (ee), and the direct aldol reaction to afford β-hydroxy ketones in high diastereoselectivity (up to 88:12 anti:syn ratio) and up to 72% ee.

Synthesis of novel chiral bisthiophene-based phosphine oxides as Lewis bases in organocatalytic stereoselective reactions / S. Rossi, M. Benaglia, R. Cirilli, T. Benincori. - In: ASYMMETRIC CATALYSIS. - ISSN 2300-4630. - 2:1(2015), pp. 17-25. [10.1515/asorg-2015-0002]

Synthesis of novel chiral bisthiophene-based phosphine oxides as Lewis bases in organocatalytic stereoselective reactions

S. Rossi;M. Benaglia;
2015

Abstract

Novel enantiomerically pure tetramethylbithiophene diphosphine oxides (tetraMe-BITIOPO) featuring differently substituted aromatic rings at the phosphorous atoms were synthesized, fully characterized and isolated in enantiomerically pure form. The new Lewis bases were tested as organocatalysts in two different reactions involving trichlorosilyl compounds. The introduction of electron donating substituents on the aromatic rings connected to the phosphine oxide groups positively affected the chemical and stereochemical catalytic efficiency of these ligands. The new catalysts were able to promote the allylation of aldehydes with allyltrichlorosilane in up to 76% yield and up to 86% enantiomeric excess (ee), and the direct aldol reaction to afford β-hydroxy ketones in high diastereoselectivity (up to 88:12 anti:syn ratio) and up to 72% ee.
organocatalysis; biheteroaromatic diphosphine oxides; chiral Lewis bases; allylation; direct aldol addition
Settore CHIM/06 - Chimica Organica
Article (author)
File in questo prodotto:
File Dimensione Formato  
asorg-2015-0002-1.pdf

accesso aperto

Tipologia: Publisher's version/PDF
Dimensione 636.59 kB
Formato Adobe PDF
636.59 kB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

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/2434/322877
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact