title: Heterodimeric Bis(amino thiol) Complexes of Oxorhenium(V) That Mimic the Structure of Steroid Hormones. Synthesis and Stereochemical Issues.
abstract: We have prepared a series of bis-bidentate complexes of rhenium that mimic the size, shape, and peripheral functionality of steroidal androgens. In a model system, we used 2D NMR and X-ray crystallographic analysis to show that adjacent N-methyl and oxo substitutents adopt an anti configuration during the coordination reaction. We have synthesized a bis-bidentate oxorhenium(V) complex whose structure and peripheral functionality mimic 5alpha-dihydrotestosterone. 2D-NMR analysis indicates that the N-methyl and oxo substituents are driven into the steroidal anti configuration (beta-N-methyl, alpha-oxo) by the beta-orientation of the methyl group equivalent to C-18. Thus, this metal complex provides a remarkable structural and stereochemical mimic of a steroid. Its in vivo stability, however, appears to be limited.
authors.affiliation: Department of Chemistry, University of Illinois, 600 S. Mathews Avenue, Urbana, Illinois 61801.
authors.forename: Roy K.
authors.initials: RK
authors.lastname: Hom
authors.forename: Dae Yoon
authors.initials: DY
authors.lastname: Chi
authors.forename: John A.
authors.initials: JA
authors.lastname: Katzenellenbogen