Despite strong repulsion between the methyl groups, the intramolecular Heck reaction of cyclohexenyl trifluoromethanesulfonate 1, available from 5‐α‐cholestan‐3‐one, proceeds in 50% yield. The product of the Heck reaction can be converted in a few subsequent steps into the cholesterol‐baccatin III hybrid 2. (Figure Presented.) Copyright © 1995 by VCH Verlagsgesellschaft mbH, Germany