Highly regioselective decarboxylative Claisen rearrangement reactions of diallyl 2-sulfonylmalonates

A quantitative structure-reactivity relationship in decarboxylative Claisen rearrangement reactions of allylic tosylmalonate esters.

First-order rate constants have been determined for the decarboxylative Claisen rearrangement reactions at 293 K of substituted methyl (E)-3-phenyl-2-propenyl 2-tosylmalonate esters, which show a linear free-energy relationship indicative of the development of positive charge on the benzylic position in the sigmatropic rearrangement transition-state.

Double decarboxylative Claisen rearrangement reactions: microwave-assisted de novo synthesis of pyridines.

Microwave-assisted double decarboxylative Claisen rearrangement of bis(allyl) 2-tosylmalonates provides substituted 1,6-heptadienes, which may be alkylated, and then converted into pyridines by ozonolysis followed by reaction with ammonia generated in situ under microwave conditions.

Transannular, decarboxylative Claisen rearrangement reactions for the synthesis of sulfur-substituted vinylcyclopropanes.

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

The Claisen Rearrangement

Synthesis of icariin from kaempferol through regioselective methylation and para-Claisen–Cope rearrangement

The hemisynthesis of the naturally occurring bioactive flavonoid glycoside icariin (1) has been accomplished in eleven steps with 7% overall yield from kaempferol. The 4'-OH methylation of kaempferol, the 8-prenylation of 3-O-methoxymethyl-4'-O-methyl-5-O-prenyl-7-O-benzylkaempferol (8) via para-Claisen-Cope rearrangement catalyzed by Eu(fod)3 in the presence of NaHCO3, and the glycosylation of...