Copper oxidation chemistry using a 19-iminopyridine-bearing steroidal ligand: (i) C5-C6 olefin difunctionalization and (ii) C1β-hydroxylation/C19-peroxidation

Samuel D Offei; Hadi D Arman; Francis K Yoshimoto

doi:10.1016/j.steroids.2022.109088

Copper oxidation chemistry using a 19-iminopyridine-bearing steroidal ligand: (i) C5-C6 olefin difunctionalization and (ii) C1β-hydroxylation/C19-peroxidation

Steroids. 2022 Oct:186:109088. doi: 10.1016/j.steroids.2022.109088. Epub 2022 Jul 11.

Authors

Samuel D Offei¹, Hadi D Arman¹, Francis K Yoshimoto¹

Affiliation

¹ Department of Chemistry, The University of Texas at San Antonio (UTSA), San Antonio, TX 78249, USA.

PMID: 35835204
DOI: 10.1016/j.steroids.2022.109088

Abstract

The Schönecker oxidation involves the 12beta-hydroxylation of 17-imino pyridine DHEA derivatives using copper and either molecular oxygen or hydrogen peroxide as the oxidant. In this study, a 19-imino pyridine DHEA derivative was synthesized and was treated with copper nitrate and hydrogen peroxide. Our results showed the difunctionalization of an olefin for delta-5 steroid substrates to yield a 5beta-hydroxylated 6alpha-nitrate ester product. In contrast, for 19-imino pyridine precursors with a 5alpha-androstane steroid backbone: a 1beta-hydroxylation and 19-peroxidation occurred to yield a 1beta-hydroxylated 19-imidoperoxoic acid product. In conclusion, new Schönecker oxidation chemistry was discovered (C5-C6 olefin difunctionalization and C1beta-hydroxylation/C19-peroxidation) when a 19-imino pyridine DHEA derivative was used as the substrate.

Keywords: Copper; Hydrogen peroxide; Oxidation; Peracid; Steroid chemistry.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't

MeSH terms

Alkenes*
Copper
Dehydroepiandrosterone / chemistry
Hydrogen Peroxide
Hydroxylation
Ligands
Nitrates*
Oxidation-Reduction
Steroids / chemistry

Substances

Alkenes
Ligands
Nitrates
Steroids
Dehydroepiandrosterone
Copper
Hydrogen Peroxide