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.

Starting from cheap chiral pool precursors camphorsulfonic acid and camphene, several imidazolium ionic liquids were synthesized in high overall yield. Both thermal and microwave-assisted­ synthesis was used in the quaternization step to obtain new chiral ionic liquids (CILs) bearing a bornyl structural motif as cation. Furthermore, these CILs were used as solvent in the Diels-Alder­ reaction of acrylic acid and cyclopentadiene and showed good yields and diastereoselectivities.