Chiral amine-imine ligands based on trans-2,5-disubstituted pyrrolidines and their application in the palladium-catalyzed allylic alkylation

Hongfeng Chen, James A. Sweet, Kin Chung Lam, Arnold L. Rheingold, Dominic V Mcgrath

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

A series of amine-imine bidentate ligands based on a trans-2,5-disubstituted pyrrolidine and pyridine moieties have been prepared. The use of these ligands in the palladium-catalyzed allylic alkylation reaction of rac-(E)-1,3-diphenylprop-2-enyl acetate is reported. The results suggest that these ligands are good catalyst precursors for the reaction. Electronic modification on the pyridine ring of the ligands does not have a significant effect on the enantioselectivity of the reaction but does on the reaction rate, while structural modification on either the pyridine or the pyrrolidine moiety affords dramatic changes on the outcome of the stereochemistry. Evidence from various studies suggested that during the palladium-catalyzed allylic alkylation reaction, nucleophilic attack onto the 1,3-diphenylallyl moiety in the transition state occurs mainly trans to the pyridine ring of the less stable conformation of the palladium complexes.

Original languageEnglish (US)
Pages (from-to)1672-1682
Number of pages11
JournalTetrahedron Asymmetry
Volume20
Issue number14
DOIs
StatePublished - Jul 29 2009

Fingerprint

Pyrrolidines
Imines
alkylation
Alkylation
Palladium
Pyridine
imines
Amines
palladium
pyridines
amines
Ligands
ligands
Stereochemistry
Enantioselectivity
rings
stereochemistry
attack
Reaction rates
Conformations

ASJC Scopus subject areas

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

Cite this

Chiral amine-imine ligands based on trans-2,5-disubstituted pyrrolidines and their application in the palladium-catalyzed allylic alkylation. / Chen, Hongfeng; Sweet, James A.; Lam, Kin Chung; Rheingold, Arnold L.; Mcgrath, Dominic V.

In: Tetrahedron Asymmetry, Vol. 20, No. 14, 29.07.2009, p. 1672-1682.

Research output: Contribution to journalArticle

Chen, Hongfeng ; Sweet, James A. ; Lam, Kin Chung ; Rheingold, Arnold L. ; Mcgrath, Dominic V. / Chiral amine-imine ligands based on trans-2,5-disubstituted pyrrolidines and their application in the palladium-catalyzed allylic alkylation. In: Tetrahedron Asymmetry. 2009 ; Vol. 20, No. 14. pp. 1672-1682.
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