Heterodimeric Bis(amino thiol) Complexes of Oxorhenium(V) That Mimic the Structure of Steroid Hormones. Synthesis and Stereochemical Issues.
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.
Hom
Roy K.
RK
Department of Chemistry, University of Illinois, 600 S. Mathews Avenue, Urbana, Illinois 61801.
Chi
Dae Yoon
DY
Katzenellenbogen
John A.
JA