RESUMO
A general protocol for the europium-catalyzed rearrangement of aryl-pentadienyl-ethers is described. The mode of rearrangement and product formation in this reaction was solely determined by the aryl substituent para to the phenol. If the para-position is occupied by a substituent, the substrate undergoes a [3,3] rearrangement to the ortho-position to form a prochiral branched diene. In turn, a free para-position in the starting material allows the reaction to proceed via a [5,5] rearrangement and leads to a linear conjugated diene product. The severely underdeveloped and synthetically valuable [5,5] rearrangement was investigated in terms of scope and mechanism.
RESUMO
Dehydrochloromethyltestosterone (DHCMT) is one of the most detected illicit used anabolic-androgenic steroids in professional sports. Therefore, a fast and accurate analysis of this substance is of great importance for a constructive fight against doping abuse. The conventional method for the analysis of this drug, GC-MSMS, is very sensitive and selective but also very time- and resource-consuming. With the presented work, a new approach for simple detection with LC-HRMSMS without any sample preparation is introduced. The method is based on the direct analysis of two newly described phase-II metabolites of the DHCMT long-term metabolite 4-chloro-18-nor-17ß-hydroxymethyl-17α-methyl-5ß-androst-13-en-3α-ol (M3). LC-HRMSMS, GC-MSMS, fractionation and derivatization experiments are combined to identify and characterize for the first time two different glucuronide-acid conjugates of this metabolite in positive human urine samples. In addition, a third glucuronide metabolite was identified, however without isomeric structure determination. The detection of these metabolites is particularly interesting for confirmation analyses, as the method is rapid and requires little sample material.
