A stereoselective synthesis of tricarbonyl‐[((1RS,2RS,4RS,5RS,6RS)‐C‐5,6,C‐η‐(5,6,7,8,‐tetramethylidenbicyclo[2.2.2]octan‐2‐ol)]iron (11),and of its tosylate 12 and benzoate 13 is reported. The bulk of the ‘endo’‐Fe(CO))3 moiety and of the ester groups in 13 renders its Diels‐Alder additions to methyl propynoate (15)), butynone (16), and 1‐cyanovinyl acetate highly ‘para’ regioselective. The cycloadditions of diene‐alcohol 11 are either ‘meta’‐ or ‘para’‐regioselective depending on the nature of the dienophile. In the presence of BF3. Et2O, the addition of 11 to methyl vinyl ketone is highly stereo‐ (Alder mode) and ‘para’‐regioselective, giving adduct 52 (tricarbonyl [((1 RS,4RS,8RS,9RS,10RS,12RS)‐C,9,10,C‐η‐(12‐hydroxy‐9,10‐dimethylidenetricyclo[6.2.2.02,7]dodec‐2(7)‐en‐4 yl methyl ketone)]iron) whose structure has been established by single‐crystal X‐ray crystallography.