Claisen rearrangement of an allyl phenyl ether with substituent groups in both ortho positions leads to the formation of a para-substituted product. Propose a mechanism for the following rearrangement.

Short Answer

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Question: Explain the mechanism for the Claisen rearrangement of an allyl phenyl ether with substituent groups in both ortho positions, leading to the formation of a para-substituted product. Answer: The Claisen rearrangement of an allyl phenyl ether with substituent groups in both ortho positions involves a [3,3]-sigmatropic rearrangement. The mechanism starts with the shift of π electrons between the allyl and phenyl group to form a new bond between the terminal allyl carbon atom and the ether O-atom, resulting in a bicyclic transition state. Next, the new C-O bond breaks to form a new π bond between the terminal carbon of the allyl group and the ether carbon, while the π bond between the phenyl and ether carbon shifts back to form a C-O bond, completing the rearrangement to form a para-substituted, γ,δ-unsaturated carbonyl compound.

Step by step solution

01

Understanding Claisen Rearrangement

The Claisen rearrangement is a [3,3]-sigmatropic rearrangement reaction of an allyl vinyl ether, which leads to the formation of a γ,δ-unsaturated carbonyl compound. In the case of allyl phenyl ethers with substituent groups in both ortho positions, the reaction takes place in such a way that it results in a para-substituted product.
02

Visualize the Initial Structure

Draw the structure of the initial allyl phenyl ether. Make sure to include the substituent groups in both ortho positions (orthogonal to the O-atom in the ether linkage).
03

Start the Rearrangement Process

In the first step of the rearrangement, the π electrons of the double bond between the allyl group and phenyl group shift to form a new bond between the O-atom in the ether linkage and the terminal allyl carbon atom, simultaneously breaking the C-O bond to form a new π bond between the phenyl and the ether carbon. This step results in a bicyclic transition state.
04

Formation of the Para-Substituted Product

In the final step, the new C-O bond formed between the terminal allyl carbon atom and the ether O-atom breaks to form a new π bond between the terminal carbon of the allyl group and the ether carbon. The π bond between the phenyl and ether carbon shifts back to form a C-O bond, completing the rearrangement. We end up with a para-substituted product, which is a γ,δ-unsaturated carbonyl compound.
05

Draw the Mechanism

Now that you understand the steps of the Claisen rearrangement, draw the complete reaction mechanism, including the movement of electrons and the formation of transition states. This will make it easier to visualize and understand the process of how the rearrangement proceeds. In summary, the Claisen rearrangement of an allyl phenyl ether with substituent groups in both ortho positions leads to the formation of a para-substituted product by undergoing a series of electron movements and bond formations.

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