Synthesis of new N-substituted chiral phosphine-phosphoramidite ligands and their application in asymmetric hydrogenations and allylic alkylations

Szabolcs Balogh, Gergely Farkas, Imre Tóth, J. Bakos

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Phosphine-phosphoramidite ligands containing a 2,4-pentanediyl backbone, BINOL moieties, and Me, Bn or Ph substituent on the nitrogen were synthesized and fully characterized. The electronic effect of the N-substituents was examined by 31P NMR of their corresponding seleno-phosphate-amide and phosphine-selenide derivatives. The new ligands together with their earlier reported derivatives were tested in the palladium catalyzed asymmetric allylic alkylation of rac-(E)-1,3-diphenylallyl acetate. Remarkably high activity (up to 1780 h-1 turnover frequency) and first order kinetics were observed by facilitating nucleophile formation. The substituent at the nitrogen and the configuration of chiral moieties had a high impact on the enantioselectivity. The new ligands were also tested in the rhodium-catalyzed asymmetric hydrogenation of methyl (Z)-α-acetamidocinnammate, dimethyl itaconate (up to 99.9% ee's) and methyl 2-acetamidoacrylate (up to 99.5% ee).

Original languageEnglish
Pages (from-to)666-673
Number of pages8
JournalTetrahedron Asymmetry
Volume26
Issue number12-13
DOIs
Publication statusPublished - 2015

Fingerprint

phosphine
alkylation
Alkylation
phosphines
Hydrogenation
hydrogenation
Ligands
ligands
Nitrogen
synthesis
Derivatives
nitrogen
Rhodium
Nucleophiles
selenides
Enantioselectivity
nucleophiles
Palladium
rhodium
Amides

ASJC Scopus subject areas

  • Organic Chemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Catalysis

Cite this

Synthesis of new N-substituted chiral phosphine-phosphoramidite ligands and their application in asymmetric hydrogenations and allylic alkylations. / Balogh, Szabolcs; Farkas, Gergely; Tóth, Imre; Bakos, J.

In: Tetrahedron Asymmetry, Vol. 26, No. 12-13, 2015, p. 666-673.

Research output: Contribution to journalArticle

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