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18.4: Reactions of Ethers - Claisen Rearrangement

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    After completing this section, you should be able to

    1. write an equation to represent the Claisen rearrangement of allyl phenyl ester.
    2. account for the formation of a specific product from a Claisen rearrangement, without giving mechanistic details.
    Key Terms

    Make certain that you can define, and use in context, the key term below.

    Claisen Rearrangements

    The Claisen rearrangement is a key organic reaction that involves the thermal rearrangement of allyl vinyl ethers to form β-aryl allyl ethers. This reaction is specific to ally aryl ethers and allyl vinyl ethers. Heating an allyl aryl ether to 250 oC causes an intramolecular rearrangement to produce an o-allylphenol.

    Example Claisen.png

    The Claisen rearrangement takes place through a concerted mechanism in which a C-C bond forms between the C3 of the allyl group and the ortho position of the benzene ring at the same time that the C-O bond of the ether breaks. This rearrangement initially produces the non-aromatic 6-allyl-2,4- cyclohexadienone intermediate which quickly undergoes a proton shift to reform the aromatic ring in the o-allylphenol product. Claisen rearrangement occurs in a six-membered, cyclic transition state involving the concerted movement of six bonding electrons in the first step. The presence of six electrons in a ring suggests that the transition state may have aromatic characteristics. The Claisen rearrangement is part of a broader class of reactions called sigmatropic rearrangements which will be discussed in more detail in Section 30-8.

    Mechanism Claisen.png

    Evidence for this mechanism was provided by performing the rearrangement with allyl group with a 14C label at C3. The product of this reaction was shown to have the 14C labeled carbon exclusively bonded to the ring.

    14C Example.png

    Allyl vinyl ethers can also undergo a Claisen rearrangement when heated to form gamma, delta -unsaturated ketones or aldehydes.

    Mechanism allyl vinyl.png

    Claisen rearrangements are rare in biological chemistry. One example is the chorismate mutase catalyzed Claisen rearrangement of chorismate (a allylic vinyl ether) to form prephenate. Prephenate is a precursor in the biosynthetic pathway of aromatic amino acids phenylalanine and tyrosine.


    Exercise \(\PageIndex{1}\)

    1) Show how you could synthesize allyl phenyl ether from allyl bromide and phenol.

    2) What would be the expected product of the following Claisen rearrangement?







    18.4: Reactions of Ethers - Claisen Rearrangement is shared under a CC BY-SA 4.0 license and was authored, remixed, and/or curated by Steven Farmer & Dietmar Kennepohl.