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Curtin-Hammett Principle: Example

The Curtin–Hammett principle states that for a reaction involving two rapidly interconverting intermediates or reactants that each irreversibly form different products, the ratio of products will depend only on the difference in free energy of the transition states leading to each product, not on the equilibrium constant between the intermediates. An example is given of species A and B in equilibrium rapidly interconverting while A forms product C and B forms D irreversibly. The principle shows that the relative stability of A and B does not affect the product ratio, only the relative transition state energies. The principle can be applied to explain selectivity in stereoselective reactions.

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Dhriti Visvanathan
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998 views

Curtin-Hammett Principle: Example

The Curtin–Hammett principle states that for a reaction involving two rapidly interconverting intermediates or reactants that each irreversibly form different products, the ratio of products will depend only on the difference in free energy of the transition states leading to each product, not on the equilibrium constant between the intermediates. An example is given of species A and B in equilibrium rapidly interconverting while A forms product C and B forms D irreversibly. The principle shows that the relative stability of A and B does not affect the product ratio, only the relative transition state energies. The principle can be applied to explain selectivity in stereoselective reactions.

Uploaded by

Dhriti Visvanathan
Copyright
© © All Rights Reserved
Available Formats
Download as DOC, PDF, TXT or read online on Scribd
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CurtinHammett principle

From Wikipedia, the free encyclopedia

The CurtinHammett principle is a principle in chemical kinetics that was proposed by David Yarrow Curtin and ouis !lack Hammett" #t states that, for a reaction that has a pair of reactive intermediates or reactants that interconvert rapidly $as is usually the case for conformers%, each &oin& irreversibly to a different product, the product ratio will depend only on the difference in the free ener&y of the transition state &oin& to each product, and not on the e'uilibrium constant between the intermediates"
()*(+*

(edit*,-ample For e-ample, &iven species A and B that e'uilibrate rapidly while A turns irreversibly into C, and B turns irreversibly into D.

K is the e'uilibrium constant between A and B, and k) and k+ are the rate constants for the formation of C and D, respectively" When the rate of interconversion between / and 0 is much faster than either k) or k+ then the CurtinHammett principle tells us that the C.D product ratio will not reflect K, but the relative ener&y of the transition states" The reaction coordinate free ener&y profile can be represented by the followin& scheme.

The ratio of products will depend only on the value labeled 11 G2 in the fi&ure. C will be the ma3or product, because the ener&y of TS1 is lower than the ener&y of TS2" #t doesn4t matter whether A is more stable than B or not, or by how much" This can be understood 'ualitatively by thinkin& what would happen if the free ener&y of A were increased, while keepin& everythin& else constant" 5n one hand, 1G)2 would become smaller, which would make k) lar&er, therefore favorin& the formation of C" 0ut on the other hand, the amount of A in e'uilibrium would decrease, because the chan&e in 1G would increase the value of K, favorin& B" These two effects cancel out, leadin& to the conclusion that the relative ener&ies of A and B don4t matter" This can also be proved al&ebraically as shown below" (edit*Derivation The rate of formation for compound C from / is &iven as

and that of D from 0 as.

with 6c the e'uilibrium constant" The ratio of the rates is then.

The product ratio can also be written as.

edit*/pplication

to stereoselective reactions

The CurtinHammett principle is used to e-plain the selectivity ratios for stereoselective reactions, such as in kinetic resolution" / typical e-ample is the followin&. a prochiral molecule binds to a chiral catalyst, formin& a pair of diastereomeric intermediates, dependin& on which face of the substrate was bound to the catalyst" These intermediates e'uilibrate rapidly $like A and B in the dia&ram above%, and each one then leads to a different enantiomer of the product throu&h the rate7determinin& step"

1.

^ Carey, Francis /"8 9undber&, :ichard ;"8 $)<=>%" Advanced Organic Chemistry Part A Structure and Mechanisms (2nd ed.). ?ew York ?"Y". !lenum !ress" #90? @7A@B7>))<=7<

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