The accepted mechanism for a rearrangement reaction is shown below. "Q Ph Ph Ph OH Ph J L G Ph Ph HO O (i) (ii) (iii) HO™ fast slow fast HQ Ph LO™ Ph Draw a curly arrow mechanism for this transformation. Sketch an energy profile for this reaction, showing approximate relative energies for the reactants, intermediates, transition states, and products. When DO™ was used as the reagent, the rate of product formation was same as for HO™. Explain why this result shows that the third step is fast and cannot be rate-determining.

Organic Chemistry
9th Edition
ISBN:9781305080485
Author:John E. McMurry
Publisher:John E. McMurry
Chapter23: Carbonyl Condensation Reactions
Section23.SE: Something Extra
Problem 28MP
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The accepted mechanism for a rearrangement reaction is shown below.
"Q Ph
(1)
(ii)
Ph
Ph
HO™
fast
Ph
Ph
HO O™
slow
Ph
aufae
.Ar²
LOH
HO™
fast
Draw a curly arrow mechanism for this transformation.
Sketch an energy profile for this reaction, showing approximate relative energies for the
reactants, intermediates, transition states, and products.
HQ Ph
(iii) When DO™ was used as the reagent, the rate of product formation was same as for HO™.
Explain why this result shows that the third step is fast and cannot be rate-determining.
Ph
(iv) Write the predicted rate equation for this mechanism, and show how it was derived.
(v) The starting diketone may have two different aryl groups, as shown below. Propose a ¹³℃
labelling experiment that would allow you to distinguish which of the two aryl groups had
migrated in this situation.
OH
AR²0-
Ar¹
C
C
Transcribed Image Text:The accepted mechanism for a rearrangement reaction is shown below. "Q Ph (1) (ii) Ph Ph HO™ fast Ph Ph HO O™ slow Ph aufae .Ar² LOH HO™ fast Draw a curly arrow mechanism for this transformation. Sketch an energy profile for this reaction, showing approximate relative energies for the reactants, intermediates, transition states, and products. HQ Ph (iii) When DO™ was used as the reagent, the rate of product formation was same as for HO™. Explain why this result shows that the third step is fast and cannot be rate-determining. Ph (iv) Write the predicted rate equation for this mechanism, and show how it was derived. (v) The starting diketone may have two different aryl groups, as shown below. Propose a ¹³℃ labelling experiment that would allow you to distinguish which of the two aryl groups had migrated in this situation. OH AR²0- Ar¹ C C
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