Hydride reduction of N-methylacridinium ion by isopropanol catalyzed by Zn(II)

ORGN 91

Yun Lu, yulu@siue.edu and Donald Endicott, dendico@siue.edu. Department of Chemistry, Southern Illinois University Edwardsville, Edwardsville, IL 62026

Alcohols can be readily oxidized via hydride transfer by NAD+ coenzyme catalyzed by alcohol deydrogenases that contain a Zn(II) ion in the active site. We report our recent study of the hydride reduction of a NAD+ model N-methylacridinium ion (MA+ClO4-) by isopropanol at reflux conditions in the presence of five different Zn(II) species, Zn(ClO4)2•6H2O, Zn(OTf)2, Zn(NO3)2, Zn(OC(O)CH3)2 and a complex [(TACD)-Zn-OH2](ClO4)2 (TACD=1,4,7,10-tetraazacyclododecane). Isolated yields of the acid-stable product of N-methylacridan (MAH) as high as 71% were observed with increasing the concentrations of the Zn(II) catalysts. In the absence of the Zn(II) catalyst, the reaction of MA+ salts of perchlorate and iodide gave rise to MAH with 7% and 40% yields, respectively. KOTf and KI were also found to catalyze the reaction. The results suggest that in the reactions studied both Zn(II) and negatively charged counter ions catalyze the reaction.