Abstract New total syntheses of hemins which are regioselectively deuteriated in the 1, 5 (2), 5 (3) or 8 (4) methyl groups are described. Syntheses of hemins 2 and 3 follow the progression from pyrromethane 12 to t-butyl tripyrrene-carboxylate hydrobromide (17 and 30) and then to a, c-biladiene dihydrobromide (19 and 31), but for reasons of economy in use of labeled monopyrroles, the o, c-biladiene dihydrobromide 40 for hemin 4 is ...