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Thermodynamic Versus Kinetic Reaction Control, Diffusion Control

Thermodynamic Versus Kinetic Reaction Control, Diffusion Control

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02/08/2014

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Thermodynamic versus kinetic reaction control
 
From Wikipedia, the free encyclopedia
Energy profile diagram for kinetic versus thermodynamic product reaction.
Thermodynamic reaction control
or
kinetic reaction control
in a chemical reaction can decide the composition in a reaction product mixture when competing pathways lead to different products and the reactionconditions influence the selectivity.The distinction is relevant when product
A
forms faster thanproduct
B
because the activation energy for product
A
is lower than that for product
B
, yet product
B
is morestable. In such a case
A
is the kinetic product and is favoured under kinetic control and
B
is the thermodynamicproduct and is favoured under thermodynamic control. 
 The conditions of the reaction, such as temperature, pressure, or solvent, affect which reaction pathway maybe favored: either the kinetically controlled or the thermodynamically controlled one. Note this is only true if theactivation energy of the two pathways differ, with one pathway having a lower E
a
 (energy of activation)than the other.Prevalence of thermodynamic or kinetic control determines the final composition of the product when thesecompeting reaction pathways lead to different products. The reaction conditions as mentioned above influencetheselectivity of the reaction - i.e., which pathway is taken.
 
Contents
[hide] 
 
o
 
o
 
Scope
In Diels-Alder reactions
The Diels-Alder reaction of cyclopentadiene with furan can produce two isomeric products. At room temperature,kinetic reaction control prevails and the less stable endo isomer 
2
is the main reaction product. At81°C and after long reaction times, thechemical equilibrium can assert itself and the thermodynamically more stable exo isomer 
1
is formed. The
exo 
product is more stable by virtue of a lower degree of steric congestion,  while the
endo 
product is favoured by orbital overlap in the transition state. 
In enolate chemistry
In the protonation of an enolate ion,the kinetic product is the enol and the thermodynamic product is a ketone or aldehyde.Carbonyl compounds and their enols interchange rapidly by proton transfers catalyzed by acids or bases,even in trace amounts, in this case mediated by the enolate or the proton source. In the deprotonation of an unsymmetrical ketone,the kinetic product is the enolate resulting from removal of the most accessible
α
-H while the thermodynamic product has the more highly substituted enolatemoiety.
 Use of low temperatures and sterically demanding bases increases the kinetic selectivity. Here, the difference in p
b
 between the base and the enolate is so large that the reaction is essentially irreversible,so the equilibration leading to the thermodynamic product is likely a proton exchange occurring during theaddition between the kinetic enolate and as-yet-unreacted ketone. An inverse addition (adding ketone to thebase) with rapid mixing would minimize this. The position of the equilibrium will depend on the countercationand solvent.
 
 If a much weaker base is used, the deprotonation will be incomplete, and there will be an equilibriumbetween reactants and products. Thermodynamic control is obtained, however the reaction remainsincomplete unless the product enolate is trapped, as in the example below. Since H transfers are veryfast, the trapping reaction being slower, the ratio of trapped products largely mirrors the deprotonationequilibrium.
In electrophilic additions
The electrophilic addition reaction of hydrogen bromide to 1,3-butadiene above room temperature leads predominantly to the thermodynamically more stable 1,4 adduct, 1-bromo-2-butene, but decreasing thereaction temperature to below room temperature favours the kinetic 1,2 adduct, 3-bromo-1-butene.
 The rationale for the differing selectivities is as follows: Both products resultfrom Markovnikov protonation at position 1, resulting in a resonance-stabilized allylic cation. The 1,4 adduct places the larger Br atom at a less congested site and includes a more highly substitutedalkene moiety, while the 1,2 adduct is the result of the attack by the nucleophile (Br
-
) at thecarbon of the allylic cation bearing the greatest positive charge (the more highly substituted carbon).

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