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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Angewandte Chemie International Edition. The migrating group attacks trans to the leaving OH group: But in my case, when there is a H shift possible, why does it not happen? From Wikipedia, the free encyclopedia.

organic chemistry – Pinacol pinacolone rearrangement – Chemistry Stack Exchange

Retrieved from ” https: Here is a link see section 2. Post as a guest Name. This is perhaps the best explanation available- chemistry.

It could be equilibrium driven. Solution In the figure below I’ve drawn the 3 isomers of cyclohexane-1,2-diol. I expected the product to be cyclohexanone but to my surprise the answer was 1-cyclopentylmethanal.

I came across this question in three different textbooks. Amritansh Singhal 5 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.

The reaction product he obtained instead he called paraceton which he believed to be an acetone dimer. Post as a guest Name. Moreover, if the migrating alkyl group has a chiral center as its key atom, the configuration at this center is retained even after migration takes place.


By using this site, you agree to the Terms of Use and Privacy Policy. In the figure below I’ve drawn the 3 isomers of cyclohexane-1,2-diol. Is the interconversion possible? By using our site, you acknowledge that you have read and understand our Cookie PolicyPrivacy Policyand our Terms of Service.

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The pinacol—pinacolone rearrangement is a method for converting a 1,2-diol to a ponacol compound in organic chemistry. Again Fittig was unable to assign a molecular structure to the reaction product which he assumed to be another isomer or a polymer.

Predominant formation of the cyclopentyl carbaldehyde indicates that our reaction must be kinetically driven. Contemporary chemists who had already adapted to the new atomic 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.

There appears to be a connection between the migration origin and migration terminus throughout the reaction.

Hence, this isomer can produce both the cyclopently carbaldehyde and cyclohexanone. Can you point us to papers that investigated the mechanism and came to this conclusion?

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. Such migrations have a strong preference for occurring by way of an anti-periplanar geometry. This suggests that the 5-membered ring product should predominate.


Pinacol rearrangement – Wikipedia

What can be the driving factor for the ring to preferentially contract? We see that there are 3 pathways leading to the 5-membered ring product and just one leading to the 6-membered ring product.

Koolman 6 Can anyone please tell me the stereochemistry. Then when one does come along, few people seem really interested in the question or answer, so I’ve kinda become more of an observer. In his second publication in he reacted paraceton with sulfuric acid the actual pinacol rearrangement. You immediately form the aldehyde after ring contraction. I never considered the cis-trans isomers. ChakravarthyKalyan Yes, as noted in my first bullet in the “Background” section of my answer, the cis and trans isomers interconvert under the conditions of the pinacol reaction.

Pinacol Rearrangement

If otherwise, ring expansion occurs, i. Sign up or log in Sign up using Google.

I’d bet that some cyclohexanone pinacllone also formed, but that it is the minor product. In these reactions, the stereochemistry of the diol plays a crucial role in deciding the major product. I forgot that the six membered ring would be puckered and not planar. In cyclic systems, the reaction presents more features of interest. Sign up using Facebook.