Mechanistic studies of La 3+-and Zn 2+-catalyzed methanolysis of aryl phosphate and phosphorothioate triesters. Development of artificial phosphotriesterase …

…, AA Neverov, JSW Tsang, RS Brown

Index: Liu, Tony; Neverov, Alexei A.; Tsang, Josephine S.W.; Brown, R. Stan Organic and Biomolecular Chemistry, 2005 , vol. 3, # 8 p. 1525 - 1533

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Citation Number: 57

Abstract

The methanolyses of a series of O, O-diethyl O-aryl phosphates (2, 5) and O, O-diethyl S-aryl phosphorothioates (6) promoted by methoxide and two metal ion systems,(La3+) 2 (− OCH3) 2 and 4: Zn2+:− OCH3 (4= 1, 5, 9-triazacyclododecane) has been studied in methanol at 25° C. Brønsted plots of the logk2 values vs. sspKa for the phenol leaving groups give βlg values of− 0.70,− 1.43 and− 1.12 for the methanolysis of the phosphates ...