Synthesis of N-[2-(2-pyridyl)ethyl]-17a-aza-D-homosteroids and their biomimetic copper-mediated ligand hydroxylations with molecular oxygen

Angéla Magyar, Bruno Schönecker, J. Wölfling, G. Schneider, Wolfgang Günther, Helmar Görls

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Starting with the oximes of 3-O-methylestrone and 3-O-methyl-13α-estrone we have synthesized 17a-aza steroids as chiral trans- and cis-fused piperidines via a Beckmann rearrangement. These could then be transformed to the corresponding N-[2-(2-pyridyl)ethyl]-17a-aza-steroids. Copper(I) complexes of these bidentate ligands bind and activate molecular oxygen. While the cis-azasteroids are inert towards hydroxylation, in the trans-series hydroxylation occurs β to the N-atom on the ring (C-16) and in the side chain: The former hydroxylation is completely stereoselective with only the (16R)-epimer being produced while the latter oxidation occurs with low stereoselectivity. The influence of how the copper(I) complexes were prepared on the oxidation behavior is discussed.

Original languageEnglish
Pages (from-to)1925-1934
Number of pages10
JournalTetrahedron Asymmetry
Volume14
Issue number13
DOIs
Publication statusPublished - Jul 4 2003

Fingerprint

Homosteroids
Biomimetics
Hydroxylation
steroids
Molecular oxygen
biomimetics
Copper
Ligands
Oxygen
copper
ligands
oxidation
piperidine
Azasteroids
oxygen
synthesis
Piperidines
Steroids
Stereoselectivity
Oxidation

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry
  • Drug Discovery

Cite this

Synthesis of N-[2-(2-pyridyl)ethyl]-17a-aza-D-homosteroids and their biomimetic copper-mediated ligand hydroxylations with molecular oxygen. / Magyar, Angéla; Schönecker, Bruno; Wölfling, J.; Schneider, G.; Günther, Wolfgang; Görls, Helmar.

In: Tetrahedron Asymmetry, Vol. 14, No. 13, 04.07.2003, p. 1925-1934.

Research output: Contribution to journalArticle

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