Abstract A variety of enantiomerically pure steroidal compounds was synthesized utilizing a sequence of Stille and Heck cross-coupling reactions and subsequent thermal 6π- electrocyclizations. Highly chemoselective Stille couplings on the triflate moiety of several 2- bromocyclohex-1-enyl triflates with cis-and trans-fused bicyclo [4.3. 0] nonenylstannanes furnished the corresponding tricyclic bromobutadienes in good to excellent yields (70–97 ...