The mechanism of aryl propargyl ether Claisen rearrangement in gas and solvent phase was investigated using DFT methods. Solvent phase calculations are carried out using N,N-diethylaniline as a solvent in the PCM model. The most favorable pathways involve a [3,3]-sigmatropic reaction followed by proton transfer in the first two steps and then deprotonation or [1,5]-sigmatropic reaction. Finally...

BACKGROUND Asymmetric introduction of fluorine alpha-to a carbonyl has become popular recently, largely because the direct fluorination of enolates by asymmetric electrophilic fluorinating reagents has improved, and as a result such compounds are becoming attractive synthons. We have sought an alternative but straightforward asymmetric method to this class of compounds, utilising the zwitterion...

The synthesis of five fused-bicyclic medium-ring lactones carrying identical ring-fusion to that in the polyether toxins is described using an enolate hydroxylation, intramolecular hydrosilation, Claisen rearrangement sequence.

Described is the construction of the N-methylwelwitindolinone C core via an efficient strategy that employs a sequential rhodium carbenoid-mediated O-H insertion, Claisen rearrangement and transannular [3+2] nitrone cycloaddition.

The substituted tricyclic pyrano[2,3-e]isoindolin-3-ones and , as the core structure of stachybotrin A, B, and C (), have been regioselectively synthesized for the first time by a short route which involved Mannich reaction and Claisen rearrangement.

Treatment of 2,2'-bis(allyloxy)-1,1'-binaphthyls with the first-generation Grubbs' carbene under MW-irradiation results in the formation of new polycyclic spiro-enones through an unprecedented RCM/Claisen sequence.

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.

Efficient syntheses are described for the synthetically important 3-methylquinoline-4-carbaldehydes 6a-h from o-nitrobenzaldehydes 1a-h employing a Wittig-olefination-Claisen-rearrangement protocol. The Wittig reaction of o-nitrobenzaldehydes with crotyloxymethylene triphenylphosphorane afforded crotyl vinyl ethers 2a-h, which on heating under reflux in xylene underwent Claisen rearrangement to...