CurtinHammett principle

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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<