Synthesis and structural elucidation of a dehydrochloromethyltestosterone metaboliteElectronic supplementary information (ESI) available. CCDC 1586619-1586622 and 1825768. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8ob00122g

The human urinary long-term metabolite "M3" (4-chloro-17β-hydroxymethyl-17α-methyl-18-norandrost-13-en-3-ol) of the common doping agent DHCMT has thus far been detected via GC/MS-MS, creating ambiguities concerning its absolute configuration. Its structure was elucidated via the synthesis of all eight possible stereoisomers with 17β-hydroxymethyl configuration. The highlights of the synthesis consist of a novel first generation approach to 4β-chloro-5β compounds as well as a divergent route which allows easy access to the remaining A-ring chlorohydrins. The identity of a human long-term metabolite of the doping agent Oral Turinabol (DHCMT) is secured by the synthesis of all probable stereoisomers.