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A New Type of Claisen Rearrangement Involving 1,3-Dipolar Intermediates. Preliminary communication

✍ Scribed by Roger Malherbe; Daniel Belluš

Publisher
John Wiley and Sons
Year
1978
Tongue
German
Weight
213 KB
Volume
61
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

During 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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