A DFT study on proton transfers in hydrolysis reactions of phosphate dianion and sulfate monoanion

B3LYP calculations were carried out on hydrolysis reactions of monosubstituted(R) phosphate dianion and sulfate monoanion. In the reacting system, water clusters (H2O)22 and (H2O)35 are included to trace reaction paths. For both P and S substrates with R = methyl group, elementary processes were calculated. While the phosphate undergoes the substitution at the phosphorus, the sulfate does at the methyl carbon. For the S substrate with R = neopentyl group, the product tert‐amyl alcohol was found to be formed via a dyotropic rearrangement from the neopentyl alcohol intermediate. For R = aryl groups, transition‐state geometries were calculated to be similar between P and S substrates. Calculated activation energies are in good agreement with experimental values. After the rate‐determining transition state of the substitution, the hydronium ion H3O+ is formed at the third water molecule. It was suggested that alkyl and aryl substrates are of the different reactivity of the hydrolysis. © 2014 Wiley Periodicals, Inc.

[1]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[2]  A. Warshel,et al.  On the Reactivity of Phosphate Monoester Dianions in Aqueous Solution: Brønsted Linear Free-Energy Relationships Do Not Have an Unique Mechanistic Interpretation , 1998 .

[3]  J. Tomasi,et al.  Ab initio study of ionic solutions by a polarizable continuum dielectric model , 1998 .

[4]  T. Brinck,et al.  Theoretical Studies of the Hydrolysis of the Methyl Phosphate Anion , 1999 .

[5]  A. Warshel,et al.  Electrostatic basis for enzyme catalysis. , 2006, Chemical reviews.

[6]  P. Kollman,et al.  Theoretical calculations of the hydrolysis energies of some high energy molecules. I. Phosphoric and carboxylic acid anhydrides , 1975 .

[7]  Jacopo Tomasi,et al.  A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics , 1997 .

[8]  A. Hengge.  Isotope effects in the study of phosphoryl and sulfuryl transfer reactions. , 2002, Accounts of chemical research.

[9]  Richard Wolfenden,et al.  Catalytic proficiency: the extreme case of S-O cleaving sulfatases. , 2012, Journal of the American Chemical Society.

[10]  Hua Guo,et al.  Supermolecule density functional calculations suggest a key role for solvent in alkaline hydrolysis of p-nitrophenyl phosphate. , 2007, Chemical communications.

[11]  K. Fukui.  Formulation of the reaction coordinate , 1970 .

[12]  W. Cleland,et al.  Enzymatic mechanisms of phosphate and sulfate transfer. , 2006, Chemical reviews.

[13]  D. Gorenstein,et al.  Stereoelectronic control in carbon-oxygen and phosphorus-oxygen bond breaking processes. Ab initio calculations and speculations on the mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme. , 1977, Journal of the American Chemical Society.

[14]  Shinichi Yamabe,et al.  A computational study of the role of hydrogen bonds in SN1 and E1 reactions , 2004, J. Comput. Chem..

[15]  S. Benkovic,et al.  Studies on Sulfate Esters. I. Nucleophilic Reactions of Amines with p-Nitrophenyl Sulfate , 1966 .

[16]  Shina Caroline Lynn Kamerlin.  Theoretical comparison of p-nitrophenyl phosphate and sulfate hydrolysis in aqueous solution: implications for enzyme-catalyzed sulfuryl transfer. , 2011, The Journal of organic chemistry.

[17]  Jacopo Tomasi,et al.  Continuum solvation models: A new approach to the problem of solute’s charge distribution and cavity boundaries , 1997 .

[18]  J. Knowles,et al.  The quest for free metaphosphate in solution: racemization at phosphorus in the transfer of the phospho group from aryl phosphate monoesters to tert-butyl alcohol in acetonitrile or in tert-butyl alcohol , 1988 .

[19]  M. Karplus,et al.  Solvent effects on the reaction coordinate of the hydrolysis of phosphates and sulfates: application of Hammond and anti-Hammond postulates to understand hydrolysis in solution. , 2001, Journal of the American Chemical Society.

[20]  W. Jencks,et al.  The Reactivity of Nucleophilic Reagents toward the p-Nitrophenyl Phosphate Dianion1 , 1965 .

[21]  Q. Cui,et al.  Does water relay play an important role in phosphoryl transfer reactions? Insights from theoretical study of a model reaction in water and tert-butanol. , 2009, The journal of physical chemistry. B.

[22]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[23]  A. Hengge,et al.  Isotope effects and medium effects on sulfuryl transfer reactions. , 2001, Journal of the American Chemical Society.

[24]  F. Cossío,et al.  Dyotropic reactions: mechanisms and synthetic applications. , 2009, Chemical reviews.

[25]  S. Buchwald,et al.  Stereochemistry of nucleophilic displacement on two phosphoric monoesters and a phosphoguanidine: the role of metaphosphate , 1984 .

[26]  Dineopentyl phosphate hydrolysis: evidence for stepwise water attack. , 2008, The Journal of organic chemistry.

[27]  D. Rinaldi,et al.  Theoretical studies of the hydroxide-catalyzed P-O cleavage reactions of neutral phosphate triesters and diesters in aqueous solution: examination of the changes induced by H/Me substitution. , 2005, The journal of physical chemistry. B.

[28]  R. Wolfenden,et al.  The rate of hydrolysis of phosphomonoester dianions and the exceptional catalytic proficiencies of protein and inositol phosphatases , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[29]  P. Kollman,et al.  Theoretical calculations of the hydrolysis energies of some "high-energy" molecules. 2. A survey of some biologically important hydrolytic reactions , 1978 .

[30]  W. Jencks,et al.  Mechanism and Catalysis of Reactions of Acyl Phosphates. I. Nucleophilic Reactions1 , 1961 .

[31]  R. Wolfenden.  Degrees of difficulty of water-consuming reactions in the absence of enzymes. , 2006, Chemical reviews.

[32]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[33]  D. Herschlag,et al.  Pyrophosphate Formation from Acetyl Phosphate and Orthophosphate Anions in Concentrated Aqueous Salt Solutions Does Not Provide Evidence for a Metaphosphate Intermediate , 1986 .

[34]  J. Fendler,et al.  Hydrolysis of nitrophenyl and dinitrophenyl sulfate esters , 1968 .

[35]  A. Hengge,et al.  Transition-State Structures for Phosphoryl- TransferReactions of p-Nitrophenyl Phosphate , 1994 .

[36]  D. Herschlag,et al.  The Substrate-Assisted General Base Catalysis Model for Phosphate Monoester Hydrolysis: Evaluation Using Reactivity Comparisons , 2000 .

[37]  A. Warshel,et al.  Phosphate Ester Hydrolysis in Aqueous Solution: Associative versus Dissociative Mechanisms , 1998 .

[38]  D. Herschlag,et al.  Alkaline phosphatase mono- and diesterase reactions: comparative transition state analysis. , 2006, Journal of the American Chemical Society.

[39]  A. J. Kirby,et al.  The Reactivity of Phosphate Esters. Monoester Hydrolysis , 1967 .