0 votes
19 views
ago in Organic Chemistry by (139k points)
What is the mechanism of the Pinacol-Pinacolone rearrangement reaction and how does it occur? Provide a step-by-step explanation of the process and give examples of substrates that can undergo this reaction.

1 Answer

0 votes
ago by (139k points)
The Pinacol-Pinacolone rearrangement is an organic reaction that involves the conversion of a vicinal diol  pinacol  to a ketone  pinacolone  in the presence of an acid catalyst. This reaction is a type of 1,2-rearrangement and was first reported by Wilhelm Rudolph Fittig in 1860. The mechanism of the Pinacol-Pinacolone rearrangement involves several steps:1. Protonation of the hydroxyl group: The reaction starts with the protonation of one of the hydroxyl groups of the vicinal diol by the acid catalyst. This step generates a positively charged oxonium ion.2. Formation of a carbocation: The oxonium ion undergoes a heterolytic cleavage, leading to the formation of a carbocation and a water molecule. The carbocation is stabilized by the neighboring carbon atom, which donates electron density through an inductive effect.3. 1,2-Migration of an alkyl or aryl group: In this step, the neighboring alkyl or aryl group migrates to the carbocation center, forming a new carbon-carbon bond. This migration results in the formation of a new carbocation at the position where the migrating group was initially located.4. Deprotonation: The carbocation formed in the previous step is deprotonated by a water molecule, leading to the formation of the final ketone product  pinacolone  and a hydronium ion.Examples of substrates that can undergo the Pinacol-Pinacolone rearrangement include:1. 2,3-dimethyl-2,3-butanediol  pinacol  rearranges to 3,3-dimethyl-2-butanone  pinacolone  in the presence of an acid catalyst.2. 1,2-cyclohexanediol rearranges to cyclohexanone under acidic conditions.3. 1,2-diphenylethane-1,2-diol rearranges to 1,1-diphenylethanone in the presence of an acid catalyst.It is important to note that the Pinacol-Pinacolone rearrangement is highly dependent on the substrate's structure and the reaction conditions. The rearrangement is favored when the migrating group is electron-donating and the carbocation formed in the process is stabilized. Additionally, the use of a strong acid catalyst and low temperatures can help promote the rearrangement.
Welcome to Sarvan Science Q&A, where you can ask questions and receive answers from other members of the community.
...