Propargyl Claisen rearrangement: allene synthesis and beyond

Propargyl Claisen rearrangement: allene synthesis and beyond.

The propargyl Claisen rearrangement is a known protocol to gain access to functionalized allenes through the [3,3]-sigmatropic transformation of propargyl vinyl ethers. The correct use of appropriate propargyl vinyl ethers as starting materials coupled with suitable reaction conditions can aid in the development of new domino methodologies in which the allenes are valuable intermediates in rout...

Gold(I)-catalyzed propargyl Claisen rearrangement.

Homoallenic alcohols are prepared from propargyl vinyl ethers using a trinuclear gold(I)-oxo complex, [(Ph3PAu)3O]BF4, as a catalyst for propargyl Claisen rearrangement at room temperature. The gold(I)-catalyzed reaction is effective for a diverse collection of propargyl vinyl ethers, including substrates containing aryl and alkyl groups at the propargylic position, and hydrogen, aryl, and alky...

Quantum mechanistic insights on aryl propargyl ether Claisen rearrangement.

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...

Synthesis of benzothiophene and indole derivatives through metal-free propargyl–allene rearrangement and allyl migration

An efficient base-catalyzed protocol for the synthesis of benzothiophene is described. The reaction proceeds via base-promoted propargyl-allenyl rearrangement followed by cyclization and allyl migration. Phosphine-substituted indoles can be synthesized by a similar strategy.

The Claisen Rearrangement