Metal-cation-mediated hydrolysis of phosphonoformate diesters: chemoselectivity and catalysis(1)

Journal of the American Chemical Society
R A MossJingzhi Tian

Abstract

Hydrolyses in D(2)O (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 mediate further hydrolytic reactions of the initially produced phosphonoformate monoesters 14, 15, 18, and 20. The origins of the P-OR/C-OR selectivity are discussed in terms of the metal cation hydroxo species likely to be present in solution and the kinetics of the reactions.

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Citations

Nov 2, 2005·Chemical Communications : Chem Comm·Nathan W Luedtke, Alanna Schepartz
Dec 15, 2015·Chemical Reviews·Yoon Jeong JangDavid G Churchill
Jan 20, 2017·The Journal of Organic Chemistry·Robert A Moss
Jul 21, 2005·Organic & Biomolecular Chemistry·Ana L Maldonado, Anatoly K Yatsimirsky
Nov 9, 2017·Beilstein Journal of Organic Chemistry·Charlotte M SevrainPaul-Alain Jaffrès
Feb 23, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Meng ZhaoZong-Wan Mao
Nov 5, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Jannick JacobsenNorbert Stock
Jun 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Nikoletta Harsági, György Keglevich
Mar 25, 2020·Chemical Reviews·Timur IslamogluOmar K Farha
Sep 7, 2005·Langmuir : the ACS Journal of Surfaces and Colloids·Kallol K GhoshG L Mundhara

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