4301-14-8Relevant articles and documents
Stereospecific synthesis of 1,2-difunctionalized buta-1,3-dienes via tandem [3,3]-[3,3] sigmatropic rearrangements
Banert, Klaus,Schlott, Jana
, p. 5413 - 5419 (2000)
Thermolysis of bis-thiocarbamates derived from but-3-yne-1,2-diols resulted in the formation of buta-1,3-dienes with carbamoylthio groups in positions 1 and 2 with good to excellent yields. The stereochemistry of the products is controlled by substituents
Cascade reactions: Sequential homobimetallic catalysis leading to benzofurans and β,γ-unsaturated esters
Gabriele, Bartolo,Mancuso, Raffaella,Salerno, Giuseppe,Costa, Mirco
, p. 1101 - 1109 (2007/10/03)
The concatenation between a Pd(0)-promoted deallylation catalytic cycle and a Pd(II)-promoted heterocyclization catalytic cycle (an example of what we have named "sequential homobimetallic catalysis") has been shown to occur starting from 1-(2-allyloxyphenyl)-2-yn-1-ols 1 to afford 2-benzofuran-2- ylacetic esters 2 and β,γ-unsaturated esters in high yields under carbonylative conditions. In view of the conceptual as well as the synthetic importance of the process, the mechanistic aspects and the synthetic scope of the reaction have been investigated in detail. All the experimental evidence is in agreement with the sequential homobimetallic mechanism, and the reaction has proven to be of general synthetic applicability.
Mechanism of the reaction of acetylene with Grignard reagents
Paellin, Vello,Otsa, Enn,Tuulmets, Ants
, p. 149 - 152 (2007/10/03)
Kinetics of the reaction between acetylene and phenylmagnesium bromide were investigated in diethyl ether in the presence of small additions of triethylamine and without a catalyst. The mechanistic scheme suggested by Grignard et al. was supplemented with the reaction of bromomagnesiumacetylene with the Grignard reagent. The rate constants for individual reactions were determined. Triethylamine catalyzes the reactions to different extents, the conversions of bromomagnesiumacetylene being the most susceptible to the catalysis. The possible ways of the action of the catalyst were discussed and the importance of nucleophilic assistance was stressed.
