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3.7.1 The Claisen Rearrangement

DOI: 10.1055/sos-SD-203-00213

Zeh, J.; Hiersemann, M.Science of Synthesis: Stereoselective Synthesis, (20113347.

The [3,3]-sigmatropic rearrangement of allyl vinyl ethers to form γ,δ-unsaturated carbonyl compounds is known as the Claisen rearrangement. This reaction was named after its discoverer Ludwig Claisen (18511930), who reported in 1912 that ethyl 2-acetylpent-4-enoate was formed during the attempted distillation of ethyl (2E)-3-(allyloxy)but-2-enoate (Scheme 1); interestingly, this is a catalyzed rearrangement since the reaction proceeds in the presence of catalytic amounts of ammonium chloride.[‌1‌]

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