Total syntheses of the bilirubin oxidation end product Z-BOX C and its isomeric form Z-BOX D.

Oxidative degradation products of bilirubin (BOXes) are biologically highly active and certain BOXes cause long-lasting narrowing of cerebral blood vessels presumably with a significant role in subarachnoid hemorrhage. Due to the fact that mode of action as well as fate of these BOXes is widely unknown, larger amounts of these bilirubin degradation end products are required. The total synthesis of colorless (Z)-3-(5-(2-amino-2-oxoethylidene)-4-methyl-2-oxo-2,5-dihydro-1H-pyrrol-3-yl)propanoic acid (BOX C) succeeds via a seven-step procedure with a total yield of 20%.

Synthesis and solution stability of water-soluble κN,κO-bis(3,5-dimethylpyrazolyl)ethanol manganese(i) tricarbonyl bromide (CORM-ONN1).

The reaction of (OC)MnBr with bis(3,5-dimethyl-1-pyrazolyl)methane yields [{(Pz)CH}Mn(CO)Br] (1). The use of tridentate heteroscorpionates such as bis(3,5-dimethyl-1-pyrazolyl)acetic acid and 2,2-bis(3,5-dimethyl-1-pyrazolyl)ethanol leads to the formation of mononuclear [(OC)Mn{(Pz)CH-CO}] (2) and [(OC)Mn{(Pz)CH-CHOH}]Br (3, CORM-ONN1). Salt-like photoCORM 3 is soluble in aqueous media up to a concentration of 200 μM, non-toxic up to an approx.