Stereoselective synthesis and application of tridentate aminodiols derived from (+)-pulegone

Tímea Gonda, Z. Szakonyi, A. Csámpai, Matti Haukka, F. Fülöp

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A library of tridentate aminodiols, derived from naturally occurring (R)-(+)-pulegone, was synthesized and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The reduction of pulegone furnished pulegol, which was transformed into allylic trichloroacetamide via Overman rearrangement of the corresponding trichloroacetimidate. The protected enamine was subjected to dihydroxylation with OsO4/NMO system resulting in a 1:1 mixture of (1R,2R,4R)- and (1S,2S,4R)-aminodiol diastereomers. After the removal of the trichloroacetyl protecting groups, the obtained primary aminodiols were transformed into secondary ones. The regioselectivity of the ring closure of the N-benzyl substituted aminodiols with formaldehyde was investigated resulting in both the 1,3-oxazine and oxazolidine rings. The tautomerism of the spiro and fused ring systems was observed and its mechanism was studied by detailed DFT analysis by employing an IEFPCM solvent model to provide a more realistic representation of the experimental conditions. The obtained potential catalysts were applied to the reaction of benzaldehyde and diethylzinc with moderate to good enantioselectivity (up to 90% ee).

Original languageEnglish
Pages (from-to)480-486
Number of pages7
JournalTetrahedron Asymmetry
Volume27
Issue number11-12
DOIs
Publication statusPublished - Jul 1 2016

Fingerprint

Oxazines
Regioselectivity
Catalysts
Enantioselectivity
rings
synthesis
Formaldehyde
Discrete Fourier transforms
catalysts
formaldehyde
closures
benzaldehyde
diethylzinc
trichloroacetamide
pulegone
oxazolidine

ASJC Scopus subject areas

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

Cite this

Stereoselective synthesis and application of tridentate aminodiols derived from (+)-pulegone. / Gonda, Tímea; Szakonyi, Z.; Csámpai, A.; Haukka, Matti; Fülöp, F.

In: Tetrahedron Asymmetry, Vol. 27, No. 11-12, 01.07.2016, p. 480-486.

Research output: Contribution to journalArticle

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