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

…, H Morales-Rojas, S Vijayaraghavan…

文献索引: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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被引用次数: 17

摘要

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 ...