A study of microwave-induced and standard thermal Overman rearrangement of selected allylic trichloroacetimidates 1a-1f, 6-8 to the corresponding acetamides 2a-2f, 9-11 is reported. The microwave-assisted rearrangement of trifluoroacetimidate 13 is also described. Using this methodology, an efficient access to versatile allylic trihaloacetamides building synthons was established.

The tetranortriterpene cipadonoid B was efficiently constructed from synthetic azedaralide in a one-pot cascade, via the underutilised ketal-Claisen rearrangement.

Pinostrobin (5-hydroxy-7-methoxyflavanone) obtained in relatively large amounts from fingerroot (Boesenbergia pandurata) was converted to its C-6 and C-8 prenylated derivatives. The Mitsunobu reaction, europium(III)-catalyzed Claisen-Cope rearrangement, and Claisen reaction coupled with cross-metathesis were used as the key steps. Using a sealed-vessel microwave reactor, the Mitsunobu and Clais...

An efficient synthesis of the 1-hydroxy-2-(prop-2'-enyl)9-anthrone is described. Selective nitration of anthraquinone, reduction to the corresponding amine, diazotization and treatment by sulfuric acid solution afforded the 1-hydroxy-9,10-anthraquinone in good yield as the key intermediate. Reaction with allyl bromide/K2CO3 and subsequent selective reduction accompanie...

Unsaturated epsilon-lactones bearing an alpha-arylsulfonyl or alpha-arylsulfoximinyl substituent undergo stereoselective transannular, decarboxylative Claisen rearrangement to give substituted vinylcyclopropanes.

The development of an enantioselective catalytic Claisen rearrangement1 remains an important yet elusive goal in chemical synthesis.2 With this objective in mind, we recently reported the acyl-Claisen rearrangement, a Lewis acid-catalyzed variant of the Bellus reaction3 that utilizes acid chlorides and allylic amines in the stereoselective synthesis of R,â-disubstituted-γ,δ-unsaturated carbonyl...

The use of a non-coordinating solvent for the aza-Claisen rearrangement of delta,epsilon-disubstituted acetimidates switches on a substrate directing effect that gives excellent stereoselectivity.