Abstract
AbstractDuring the reaction of allyl ethers, allyl sulfides and allyl selenides with in situ prepared dichloroketene (1), 2 competing pathways are observed. Besides [2+2]‐cycloaddition, an unprecedented [3,3]‐sigmatropic (Claisen) rearrangement via a 1,3‐dipolar intermediate takes place. It leads to O‐, S‐ or Se‐esters of α,α‐dichloro‐γ, δ‐unsaturated acids containing an inverted allylic group. Starting from cyclic n‐membered α‐vinyl‐substituted ethers, lactones with n+4‐membered rings are formed. A very facile synthesis of the naturally occurring macrolides (±)‐phoracantholide I (10) and (±)‐phoracantholide J (11) illustrates the synthetic utility of this new ‘ketene’ Claisen rearrangement.
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