18 Mar pinacol–pinacolone rearrangement. methyl migration. pyridinyl migration. The pinacol rearrangement is a well-known reaction in which a glycol. 15 Mar Pinacol-pinacolone rearrangements. Mechanism ♢ Mechanism of the pinacol rearrangement of a symmetrical glycol CH3 CH3 CH3 CH3 _. 10 Oct Pinacol-Pinacolone rearrangement over solids supported metal ion catalysts. Article (PDF Available) in Indian Journal of Chemical Technology.

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Is the interconversion possible?

But I am not able to find the sterochemistry of the reaction. Contemporary chemists who had already adapted to the new pinacok weight reality did not fare better.

He also wrongly believed acetone to be an alcohol which he hoped to prove by forming a metal alkoxide salt. This reveals another interesting feature of the reaction, viz.

By clicking “Post Your Answer”, you acknowledge that you have read our updated terms of serviceprivacy policy and cookie policyand that your continued use of the website is subject to these policies. Although Fittig pinxcolone published about the pinacol rearrangement, it was not Fittig but Aleksandr Butlerov who correctly identified the reaction products involved.

The isomer on the left is the axial, axial trans isomer, the isomer in the middle is the equatorial, equatorial trans isomer, and then on the right rearrahgement the axial, equatorial cis isomer. Zhe A mistake on my part.


This answer implies a concerted mechanism, while the mechanism is usually written stepwise. Sign up using Facebook. Sign up or log in Sign up using Google.

However, in the cases discussed where the ring degraded, there was not an option for hydride shift as the alpha carbon containing hydroxyl group was lacking an H atom. Post as a guest Name. Some of the problems during the determination of the structure are because carbon skeletal rearrangements were unknown at that time and therefore the new concept had to be found.

Annales de chimie et de physique. Sign up or log in Sign up using Google. Butlerov theory allowed the structure of carbon atoms in the molecule to rearrange and with this concept a structure for pinacolone could be found.

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Pinacol Rearrangement | Pinacol Rearrangement Mechanism | [email protected]

By using this site, you agree to the Terms of Use and Privacy Policy. Justus Liebigs Annalen der Chemie und Pharmacie. Post as a guest Name. You immediately form the aldehyde after ring contraction. There just don’t seem to be as many interesting organic questions these days. Your question is essentially why the C-C bond migrates instead of the C-H bond, right?


Angewandte Chemie International Edition. In that example, there is no stereocentre.

Pinacol Rearrangement

pjnacolone An alkyl group which reaarrangement situated trans- to the leaving —OH group alone may migrate.

Rearrangement of this isomer can only produce the cyclopentyl derivative. The driving force for this rearrangement step is believed to be the relative stability of the resultant oxonium ion, which has complete octet configuration at all centers as opposed to the preceding carbocation.

In the case of cyclohexane-1,2-diol, if a protonated hydroxyl group departed, a seconday carbocation would form.

organic chemistry – Pinacol pinacolone rearrangement – Chemistry Stack Exchange

Rearrangememt formation of the cyclopentyl carbaldehyde indicates that pjnacolone reaction must be kinetically driven.

Shouldn’t the intermediate carbocation be stable in a six membered ring rather than a five membered ring? You may want to check out this answer. Questions Tags Users Badges Unanswered. This reaction was first described by Wilhelm Rudolph Fittig in of the famed Fittig reaction involving coupling of 2 aryl halides in presence of sodium metal in dry ethereal solution.