scholarly journals Pentavalent Organo-Vanadates as Transition State Analogues for Phosphoryl Transfer Reactions

2000 ◽  
Vol 122 (41) ◽  
pp. 9911-9916 ◽  
Author(s):  
June M. Messmore ◽  
Ronald T. Raines
Keyword(s):  
Transition State ◽  
Transfer Reactions ◽  
Phosphoryl Transfer ◽  
Transition State Analogues

Silatranyl-nucleosides: transition state analogues for phosphoryl transfer reactions

2001 ◽  
Vol 42 (30) ◽  
pp. 4979-4982 ◽  
Author(s):  
Bianca R Sculimbrene ◽  
Raymond E Decanio ◽  
Brandon W Peterson ◽  
Emily E Muntel ◽  
Edward E Fenlon
Keyword(s):  
Transition State ◽  
Transfer Reactions ◽  
Phosphoryl Transfer ◽  
Transition State Analogues

The acidity of β-phosphoglucomutase monofluoromethylenephosphonate ligands probed by NMR spectroscopy and quantum mechanical methods

2016 ◽  
Vol 94 (11) ◽  
pp. 902-908 ◽  
Author(s):  
Stephanie M. Forget ◽  
Eric A.C. Bushnell ◽  
Russell J. Boyd ◽  
David L. Jakeman
Keyword(s):  
Nmr Spectroscopy ◽  
Transition State ◽  
Quantum Mechanical ◽  
Phosphoryl Transfer ◽  
Quantum Mechanical Calculations ◽  
Transition State Analogues ◽  
Mechanical Methods ◽  
Insight Into ◽  
Computational Quantum

We recently described the binding of 1-β-phosphonomethylene-1-deoxy-d-glucopyranose, (S)-1-β-phosphonofluoromethylene-1-deoxy-D-glucopyranose (βG1CFSP), and (R)-1-β-phosphonofluoromethylene-1-deoxy-d-glucopyranose (βG1CFRP) to the enzyme β-phosphoglucomutase as transition state analogues of phosphoryl transfer through formation of stable MgF3− and AlF4− complexes (Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 12384). Herein, we describe in detail the five-fold difference in acidity (pKa2) for the (S)- and (R)-configured diastereomeric fluorophosphonates through a series of NMR spectroscopy experiments. The differences in acidity were corroborated using computational quantum mechanical calculations to determine structures of lowest energy conformers and provide insight into why the (S) isomer is substantially more acidic.

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