Differentiation of stereoisomeric steroids by reactions with phosphenium ions.
A chemical ionization method is reported for distinction of diastereomeric hydroxysteroids by using Fourier-transform ion cyclotron mass spectrometry (FT-ICR). Certain phosphenium ions are demonstrated to react with stereoisomeric steroids to yield qualitatively different product ions. For example, 1,3,5(10)-estratriene-3,16beta,17beta-triol (cis-estriol) reacts with the dimethoxy phosphenium ion to form a diagnostic product ion (not formed for the trans-estriol) through addition followed by the loss of two molecules of methanol. In an analogous manner, the 1,3-dioxolan-2-phosphenium ion produces a diagnostic product ion through the loss of ethylene glycol from the adduct of cis-estriol only. The 1,3,5(10)-estratriene-3,16alpha,17beta-triol (trans-estriol), on the other hand, reacts with each phosphenium ion only via hydroxide abstraction-initiated pathways that indicate the presence of at least two hydroxyl groups in the molecule. These specific reactions take place for all hydroxysteroids examined, independent of their stereochemistry. Another isomer pair, cholestan-3alpha,5alpha-diol (cis-cholestandiol) and cholestan-3beta,5alpha-diol (trans-cholestandiol), is differentiated based on selective elimination of water only from the adduct of the cis-isomer. However, the method does not allow distinction between the stereoisomeric 5beta-pregnane-3alpha,17alpha,20alpha-triol and 5beta-pregnane-3alpha,17alpha,20beta-triol. The different reactivities of the three pairs of steroid isomers and of each diastereomeric compound pair are rationalized by reaction enthalpies and steric effects based on straightforward and predictable reaction mechanisms.
Petucci
Chris
C
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393, USA.
Guler
Leo
L
Kenttämaa
Hilkka I
HI
D004083:Cholestanol / Q000031:analogs & derivatives* / Q000737:chemistry; D017357:Cyclotrons; D004964:Estriol / Q000737:chemistry; D005583:Fourier Analysis; D007202:Indicators and Reagents; D013058:Mass Spectrometry; D008958:Models, Molecular; D009943:Organophosphorus Compounds / Q000737:chemistry; D013237:Stereoisomerism; D013256:Steroids / Q000737:chemistry* / Q000302:isolation & purification
D007202:Indicators and Reagents; D009943:Organophosphorus Compounds; D013256:Steroids; C028680:cholestane-3,27-diol; D004083:Cholestanol; D004964:Estriol