Linear Free Energy Relationship Analysis of Transition State Mimicry by 3-Deoxy-d-arabino-heptulosonate-7-phosphate (DAHP) Oxime, a DAHP Synthase Inhibitor and Phosphate Mimic

Biochemistry ◽  
2017 ◽  
Vol 56 (4) ◽  
pp. 592-601 ◽  
Author(s):  
Naresh Balachandran ◽  
Frederick To ◽  
Paul J. Berti
Keyword(s):  
Free Energy ◽  
Transition State ◽  
Linear Free Energy Relationship ◽  
Dahp Synthase ◽  
Relationship Analysis ◽  
Linear Free Energy ◽  
Synthase Inhibitor

Linear free energy relationship and kinetic isotope effects as measures for the transition-state variation — A case of the neophyl system

2005 ◽  
Vol 83 (9) ◽  
pp. 1606-1614 ◽  
Author(s):  
Salai Cheettu Ammal ◽  
Hiroshi Yamataka
Keyword(s):  
Free Energy ◽  
Transition State ◽  
Density Functional ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Single Step ◽  
Linear Free Energy Relationship ◽  
Linear Free Energy ◽  
Kinetic Isotope ◽  
State Variation

Ab initio calculations at the MP2/6-31G* level and density functional theory (B3LYP/6-311+G**) calculations have been performed on acid-catalyzed ionizations of substituted neophyl alcohols to investigate whether a variation of the transition-state (TS) structure is reflected in the kinetic isotope effects (KIE) and linear free energy relationship. The effect of substituents on KIEs, TS structures, and activation and reaction energies was calculated. This study revealed that a curved Brønsted-type plot could arise for a single-step process from the variation of TS structure with the substituent, whereas the Hammett plots with a dual-parameter treatment can not detect such TS variation. The variation of KIEs at various positions of neophyl alcohol reflects the variation of TS structures in a manner consistent with the More O'Ferrall – Jencks type reaction diagram analyses.Key words: transition-state variation, substituent effect, kinetic isotope effect, linear free energy relationship.

scholarly journals Linear Free-Energy Relationship Analysis of a Catalytic Desymmetrization Reaction of a Diarylmethane-bis(phenol)

2010 ◽  
Vol 12 (12) ◽  
pp. 2794-2797 ◽  
Author(s):  
Jeffrey L. Gustafson ◽  
Matthew S. Sigman ◽  
Scott J. Miller
Keyword(s):  
Free Energy ◽  
Linear Free Energy Relationship ◽  
Relationship Analysis ◽  
Linear Free Energy
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