Lithium-catalyzed hydroxide attack at the carbon atom of methyl phosphate

Journal of the American Chemical Society

Volumn 126, Issue 28, 2004, Pages 8646-8647

  Wolfenden, Richard ^a   Zhao, Frances ^a  

^a UNIVERSITY OF NORTH CAROLINA SCHOOL OF MEDICINE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; LITHIUM; PHOSPHATE;

AQUEOUS SOLUTION; ARTICLE; CATALYSIS; CONCENTRATION (PARAMETERS); HYDROLYSIS; REACTION ANALYSIS; TEMPERATURE DEPENDENCE;

ANIONS; CARBON; CATALYSIS; HYDROXIDES; LITHIUM; PHOSPHATES; PHOSPHORIC ACID ESTERS;

EID: 3242665916     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0473586     Document Type: Article

References (12)

1. Bunton, C. A.; Llewellyn, D. R.; Oldham, K. G.; Vernon, C. A. J. Chem. Soc. 1958, 1958, 3574.
2. Kirby, A. J.; Varvoglis, A. G. J. Am. Chem. Soc. 1967, 89, 415.
3. Lad, C.; Williams, N. H.; Wolfenden, R. Proc. Natl. Acad. Sci. U.S.A. 2003, 100, 5607.
4. Robinson. R. A.; Stokes, R. H. Electrolyte Solutions, 2nd ed.; Butterworths: London, 1959; pp 510-511.
5. Abell, K. W. Y.; Kirby, A. J. Tetrahedron Lett. 1986, 27, 1085.
6. Grzyska, P. K.; Czyryca, P. G.; Golightly, J.; Small, K.; Larsen, P.; Hoff, R. H.; Hengge, A. C. J. Org. Chem. 2002, 67, 1214.
7. Stephan, E. F.; Miller, P. D. J. Chem. Eng. Data 1962, 7, 501.
8. It would be of interest to compare the leaving group activity of the presumed lithium phosphate dianion with the leaving group activities of other anions, with respect to their ease of displacement from methane by the hydroxide ion. But since the catalytic effect of lithium hydroxide shows no sign of saturation even at its solubility limit (Figures 1 and 2), that reactivity lex can be estimated only as a lower limit.
9. eq for glycogen phosphorylation is approximately unity (Hestrin, S. J. Biol. Chem. 1949, 179, 943), but under the conditions that typically prevail in mammalian tissue, the concentration of inorganic phosphate so greatly exceeds the concentration of glucos 1-phosphate that this reaction proceeds entirely in the direction of phosphorolysis.
10. Pyridoxal phosphate is an essential cofactor for glycogen phosphorylase. Its position in the crystal structure suggests that it is (just) close enough to the reacting substrates to furnish a phosphoryl group that acts as a general base: (a) Sygusch, J.; Madsen, N. B.; Kasvinski, P. J.; Fletterick, R. J. Proc. Natl. Acad. Sci. U.S.A. 1977, 74, 4757.
11. (b) Weber, I. T.; Johnson, L. N.; Wilson, K. S.; Yeates, D. G.; Wild, D. L.; Jenckins, J. A. Nature (London) 1978, 274, 433.
12. Other evidence suggests that this may be an oversimplification however: (c) Withers, S. G.; Shechosky, S.; Madsen, N. B. Biochem. Biophys. Res. Commun. 1982, 108, 322.