Metal-Cation-Mediated Hydrolysis of Phosphonoformate Diesters: Chemoselectivity and Catalysis1

…, H Morales-Rojas, S Vijayaraghavan…

Index: Moss, Robert A.; Morales-Rojas, Hugo; Vijayaraghavan, Saketh; Tian, Jingzhi Journal of the American Chemical Society, 2004 , vol. 126, # 35 p. 10923 - 10936

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Citation Number: 17

Abstract

Hydrolyses in D2O (pD 1.7-3.1) of dimethyl (7), methyl phenyl (8), phenyl methyl (9), and diphenyl (10) phosphonoformate diesters are substantially accelerated by Ce (IV), Th (IV), Zr (IV), and Hf (IV) cations. Chemoselectivity is observed, whereby Zr (IV) and Hf (IV) principally direct P-OR hydrolysis, whereas Th (IV) and Ce (IV) mainly direct C-OR hydrolysis. Leaving group efficiency (OMe vs OPh) modulates the chemoselectivity. The metal cations also ...